Polymer Testing 100 (2021) 107270

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Incorporation of carboxyl and amino functionalized carbon quantum dots

in thin film membrane for nanofiltration
Nur Hafizah Zainal Abidin a, Siti Nur Alwanie Shafie a, Hazwani Suhaimi b, Nonni
Soraya Sambudi a, c, *, Nik Abdul Hadi Sapiaa Md Nordin a, c
a
Department of Chemical Engineering, Universiti Teknologi PETRONAS, Seri Iskandar, Perak, 32610, Malaysia
b
Faculty of Integrated Technologies, Universiti Brunei Darussalam, Tungku, Link Road BE1410, Brunei Darussalam
c
Centre of Urban Resource Sustainability (CUReS), Universiti Teknologi PETRONAS, Seri Iskandar, Perak, 32610, Malaysia

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

Keywords: Fabrication of thin film nanocomposite membrane (TFN) with carbon quantum dots (CQDs) as nanofiller has
Carbon quantum dots gained a wide attention due to the promising properties of the CQDs to enhance the membrane permeability.
Rice husks Synthesis of CQDs and their functionalization with both carboxyl and amino groups are originated from rice
Functionalization
husks as the precursor. Fourier-Transform Infrared Spectroscopy (FTIR) analysis shows that CQDs contain
Polyamide
oxygen-containing groups that allow hydrogen bonding with water molecules. Zeta potential shows that the
Hydrophilicity
incorporation of CQDs produces highly negative charged membranes, while Field Emission Scanning Electron
Microscopy (FESEM) and Atomic Force Microscopy (AFM) results indicate that the introduction of the nano­
particles alters the surface properties of the fabricated membranes. Photoluminescence (PL) analysis proves that
CQDs are present in the polyamide (PA) layer which describes the unique characteristic of the CQDs. The
presence of CQDs in TFN membranes assists in enhancing the performance of pristine thin film composite (TFC)
membrane in both flux and salt rejection with values around 35 L/m2 h and 90%, respectively.

1. Introduction incorporation of nanomaterials into the active polyamide layer to

Nanofiltration (NF) membrane has gained wide attention in mem­
brane separation process for water treatment due to their properties of
having higher rejection of solutes from the feed solution and simplicity
in setup [1]. NF has become an option for water treatment not only for
wastewater but also for desalination process as this technology con­
sumes less energy as well as shows promising performance in terms of
higher water flux [1,2]. Some factors that affect the performance of
nanofiltration are operating conditions, membrane characteristics and
characteristics of the feed. Most commercial membrane used for NF is
thin film composite (TFC) membranes which have gained attention in
recent years in membrane development to enhance their performance in
water and wastewater treatments. TFC membrane consists of two layers
which are top layer and bottom layer, known as the substrate, formed
via interfacial polymerization (IP) process [2]. The application of thin
film nanocomposite (TFN) membrane is an emerging development in
water separation process owing to the limitation of existing TFC mem­
branes. The development of TFN membranes mainly focus on the
enhance the performance of the membrane [3]. Recently, there are re­
searches that utilize the TFN membranes in water treatment using
nanomaterials as the nanofiller in the active layer [4]. However, larger
size of particles typically more than 100 nm lead to polymer bulk, thus
affecting active layer’s transfer ability and form brittle membrane [5].
The application of CQDs and other nanoparticles in thin film nano­
composite (TFN) membrane for water treatment have gained attention
in numerous researches due to their excellent hydrophilicity, smaller
sizes (less than 10 nm) that enable them to be easily dispersed in
membrane polymer and also their tunable surface properties [6]. It was
also reported that introduction of nanoparticles into the active layer of
thin film membrane could improve the performance of membrane in
water treatment [7]. This observation is attributed to the fact that
incorporation of nanoparticles could create water channel in active layer
due to hydrophilic properties of the nanoparticles [8]. The incorporation
of nanoparticles during interfacial polymerization process creates low
resistance for water transport as they actively react with the aqueous
phase of active layer [9].

* Corresponding author. Centre of Urban Resource Sustainability (CUReS), Universiti Teknologi PETRONAS, Seri Iskandar, Perak, 32610, Malaysia.
E-mail address: soraya.sambudi@utp.edu.my (N.S. Sambudi).

https://doi.org/10.1016/j.polymertesting.2021.107270
Received 6 January 2021; Received in revised form 2 May 2021; Accepted 16 May 2021
Available online 10 June 2021
0142-9418/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
N.H. Zainal Abidin et al.
Table 1
Selected studies on nanoparticles incorporation in membrane.
Nanoparticles Observation
Graphene oxide Reduced water contact angle from 83.4 to 76.2 .
◦ ◦
Enhanced water flux of 20% compared to pristine
membrane
Silica dioxide Increased negative charges of the PA layer. Higher
(SiO2) flux and rejection of almost 50% of salts when treated
with oily wastewater
Titanium dioxide Smoother surface when increasing the content of
(TiO2) TiO2. Rejection of NaCl increased from 70% to 80%
upon increasing the amount of TiO2.
Zeolite The water permeability was doubled in TFN
compared to TFC membrane. Rejection of 93% of
MgSO4 at 150 psi but no change in rejection of NaCl.
Agglomeration was observed in PA layer.
Graphene oxide TFN membrane exhibited higher hydrophilicity than
the pristine membrane. Incorporation of 0.2 g/m2 of
GO resulted in rejection of 95% and 97% of Na2SO4
and MgSO4, respectively. 31% higher water flux in
TFN than in pristine membrane.
A study by Li et al. [10] shows that incorporation of 0.02 wt% of
carbon dots in polyamide layer of reverse osmosis membrane exhibited
excellent performance with flux of 87.1% and salt rejection of about
98% compared to the membrane without introduction of nanoparticles.
In addition, the incorporation of sodium functionalized carbon dots was
also applied in forward osmosis (FO) membrane as reported by Guo et al.
[11]. The investigation resulted in 29 LMH of FO water flux which was
considered quite high in FO application. In 2014, Bano et al. [12] re­
ported the performance of TFN membrane embedded with certain
amount of graphene oxide (GO) nanoparticles. Notably, the perfor­
mance of the composite membrane shows that the flux increases
compared to the pristine membrane. By the increment of GO amount to
0.2 wt%, the flux increases up to 22 L/m2 h while salt rejection can be
maintained beyond 80%. On the other hand, a study on the incorpora­
tion of MXene on PSf support shows that more hydrophilic membranes
can be obtained when the amount of MXene increases [13]. This is
shown by the contact angle of membrane that declines from 86.9 to
78.4◦ . The addition of other nanoparticles in membrane can be sum­
marized in Table 1.
The selection of nanoparticles to be incorporated in active layer of
TFN membrane is one of the significant factors to ensure better perfor­
mance in water treatment. Some studies have utilized the application of
CQDs in membrane to observe the effect of CQDs towards the membrane
performance. A study by Yuan et al. [9] implies that the introduction of
CQDs in PA layer of nanofiltration membrane enhances the water flux by
58% compared to pristine membrane. It was also reported that CQDs
improved the water flux of nanofiltration membrane about 5–6 times of
the pristine membrane [18].
The synthesis of CQDs from waste biomass is widely studied in
various researches due to the availability of the wastes as well as the
intention to turn the wastes into more valuable products [8,9]. Rice
husks are abundantly available in rice milling industry. These wastes can
be utilized as precursor in CQDs’ synthesis as rice husks contain about
80% organic materials in which carbon, oxygen and hydrogen are pre­
sent as the major elements [19]. Apart from that, rice husks are usually
left as byproduct in dehusking process because of their hard structures,
hence they are not easily decomposed by bacteria [10]. Thus, rice husks
are the most suitable precursors to synthesize CQDs in a facile way.
In addition, functionalization of CQDs with certain functional groups
also becomes an emerging step in the development of CQDs for various
applications [20]. Functionalization is one of the modifications of con­
ventional CQDs to alter the structure of CQDs as well as their properties.
In a study by Freitas et al. [21], CQDs were functionalized with amino
group for biosensing application. The modification resulted in CQDs
with spherical dimension and uniform dispersion, having average
diameter of 4.11 nm [13]. Furthermore, functionalization agent has the
Polymer Testing 100 (2021) 107270
role in tuning the functional groups in CQDs’ structure as it enlarges the
band gap between Highest Occupied Molecular Orbital (HOMO) and
Ref. Lowest Unoccupied Molecular Orbital (LUMO) for electron excitation
[22].
[14]
It was reported that functionalization was able to tune the band gap
in CQDs’ structure, inducing blue shift emission, and increased electron
[15] density [23]. The modified carbon nanoparticles also exhibit
well-defined sizes and a convenient synthetic method, thus it allows
[16]
carbon dots production in large scale. Studies have included the syn­
thesis of carbon nanoparticles from polyethylene glycol and camphor,
carbon nanomaterials from commercial mesophase pitches, graphene
[17] oxide from iminodiacetonitrile and glucose, carbon quantum dots from
carbohydrates, and colloidal carbon spheres from glucose [24]. Carbon
dots can be modified through condensation reaction between carbonyl
[12] and amino groups by several aromatic molecules such as o-phnylene­
diamine, 2,3-diaminoaphthalene and 1,8-diaminoaphthalene [25].
These polyaromatic molecules will modify the conjugated domain of
carbon dots to alter the resulting band gap [26]. This amino function­
alized carbon dots exhibit several enhanced properties, such as dis­
persibility of the nanoparticles. Functionalization using carboxyl and
amino functional groups form a thin insulating capping layer that pre­
vent from impurities adhesion on the surface of carbon dots [27].
Hence, in this study, a new approach in utilizing functionalized rice
husks-derived CQDs is presented, and the performance is expected to
improve compared to the pristine membrane. Synthesis of CQDs and
their functionalization with both carboxyl and amino groups were
originated from rice husks as the precursor. Then, thin polyamide (PA)
layer incorporated with carboxyl and amino functionalized CQDs were
formed on polysulfone (PSf) membrane support. The presence of CQDs
in TFN membranes enhanced the performance of pristine thin film
composite (TFC) membrane in both flux and salt rejection with values
around 35 L/m2 h and 90%, respectively.
2. Materials and methods
2.1. Materials
Rice husks were obtained from Jabatan Pertanian Negeri Perak,
Malaysia. Hydrochloric acid (HCl, ̴ 37%, Code: H/1200/PC17) was
purchased from Fischer Scientific U.K. In addition, ethylenediamine
(CAS-No 107-15-3) and ascorbic acid (CAS-No 50-81-7) were obtained
from Merck Germany and HmbG Chemicals, respectively. In membrane
fabrication, polysulfone (PSf) pellets obtained from LG Low Ltd were
used as polymer. N-methyl-2-pyrollidone (NMP, Merck) acted as mem­
brane solvent and polyvinylpyrrolidone (PVP, Aldrich) K30 of Mw
40,000, was used as a pore forming agent for the substrate. N-heptane
(Merck), piperazine (PIP, Sigma Aldrich) and trimesoyl chloride (TMC,
Aldrich) monomers were used during interfacial polymerization to form
polyamide layer. De-ionized (DI) water (18.2 MΩ) from PureLab Flex
was utilized for the whole experiment. Sodium chloride (NaCl, Merck),
calcium chloride (CaCl2, R&M Chemical), magnesium chloride (MgCl2,
Supelco), copper (II) sulphate (CuSO4, Bendosen), and sodium phos­
phate (Na3PO4, Acros Organics) were employed to prepare aqueous salt
solution for salt rejection determination in membrane performance
testing.
2.2. Synthesis of CQDs
Rice husks were pretreated before the synthesis of CQDs to ease
carbonization during hydrothermal reaction [28]. In pretreatment pro­
cess, 1 g of rice husks was washed with DI water to get rid of any resi­
dues. Then, they were dried overnight in oven at 60 ◦ C before blended
into powders. The blended rice husks were then cleansed with 0.1 M HCl
to remove inorganic impurities. The treated rice husk powders were
again rinsed with DI water and dried in the oven at 60 ◦ C. For hydro­
thermal process, temperature of 190 ◦ C was selected based on a study by
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N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

similar to TFN fabrication methods, except for aqueous phase did not
contain CQDs as additives. The prepared membranes were analyzed
using Fourier Transform Infrared (FTIR), Field Emission Electron Mi­
croscopy (FESEM), Atomic Force Microscopy (AFM), zeta potential,
photoluminescence (PL), pore distribution, and contact angle analyses.

2.4. Characterizations

Perkin Elmer Spectrum One Spectrophotometer was used for FTIR

analysis while UV–Visible spectra of the samples were obtained using
Agilent Technologies Cary Series UV–Vis. In addition, PL spectra were
obtained using Maya2000 Pro Spectrometer with 390 nm wavelength of
excitation. The high resolution imaging of each CQDs sample was per­
formed using Zeiss Libra 200FE High Resolution Transmission Electron
Microscopy (HRTEM) and the average particle sizes were determined
using ImageJ software (measurement of 60 particles was analyzed). X-
Ray Diffraction (XRD) analysis was done using PANalytical X’Pert Pro
diffractometer with 0.02◦ step size while thermal stability of CQDs was
Fig. 1. Membrane filtration setup.
analyzed using TA Instruments Q-5015 thermogravimetric analyzer
using nitrogen from 25 to 800 ◦ C with a scan rate of 10 ◦ C per minute. On
Lin et al. [29] to synthesize both carboxyl and amino functionalized
the other hand, X-Ray Photoelectron Spectrometer (XPS) analysis was
CQDs. The carboxyl and amino functionalized CQDs were denoted as
performed using Thermo Scientific K-Alpha to determine the elemental
CCQDs and NCQDs, respectively. 100 mg of rice husk powders was
composition in the samples. FESEM analysis was performed using
transferred into Teflon lined autoclave together with 10 ml of ethyl­
VPFESEM, Zeiss Supra55 VP to observe the morphology of membrane
enediamine (EDA) or 2.5 ml of ascorbic acid for NCQDs and CCQDs,
while AFM analysis was done to determine the physical characteristics
respectively [30]. Hydrothermal reaction was conducted for 12 h. After
such as surface roughness of membrane samples using AFM equipment
that, the mixture was cooled down to room temperature for a day before
(Model: NanoNavi E-Sweep). Zeta potential analysis was done to
filtered using vacuum filtration. The filtrate was centrifuged at 4000
analyze the surface charges of membrane samples using Malvern,
rpm to obtain the supernatant containing CQDs. The CQDs were again
Zetasizer Nano ZSP in which the measurements were carried out under
purified using visking tubing (Cellulose 10 M) against DI water for 24 h.
pH 6.0 ± 0.2 with the samples immersed in 1.0 mM KCl solution at 25 ±
The obtained functionalized CQDs were characterized with
0.5 ◦ C. The pore distribution analysis was done using capillary flow
High-resolution transmission electron microscopy (HRTEM),
porometer (Model: CFP-1200AEL, Porous Material Inc, USA). The con­
Fourier-transform infra-red spectroscopy (FTIR), Ultraviolet–visible
tact angle of membrane was measured using goniometer (Model: Rame
(UV–Vis), and photoluminescence (PL) analyses.
Heart; 260) to determine the wettability of membrane surface.

2.3. Membrane fabrication 2.5. Evaluation of membrane performance

2.3.1. Fabrication of PSf support The water flux and salt rejection of the fabricated thin film mem­
PSf substrate was prepared by phase inversion technique. 1 wt% of branes were analyzed using dead-end filtration system under nitrogen
PVP was added into dope solution [31]. The dope solution was prepared atmosphere. TFC and TFN membranes were firstly compacted at trans-
by dissolving PVP in NMP solvent followed by adding 15 wt% of PSf membrane pressure of 0.8 MPa or 8 bar with DI water for 1 h. All the
polymer [31]. Then, the solution was stirred continuously until homo­ membrane samples were cut into circular effective area of 13.86 cm2
geneous polymer solution was obtained. After that, the substrate was before being placed in the filtration cell (Sterlitech HP4750). The ex­
casted on glass plate using a membrane knife. The fabricated substrate periments were then performed by preparing 1000 ppm of NaCl, CaCl2,
was then kept for 30 s at room temperature before being immersed in a MgCl2, CuSO4, and Na3PO4 solutions at operating pressure and tem­
water coagulation bath. The obtained PSf support was rinsed with DI to perature of 0.6 MPa or 6 bar and 25 ◦ C, respectively. Membrane water
remove excess solvent then keeping wet before further use. flux and permeability were measured using the following equations (1)
and (2), respectively:
2.3.2. Fabrication of TFN membrane V
Thin film nanocomposite (TFN) membrane was prepared through J= (1)
t × Am
interfacial polymerization (IP) technique between piperazine (PIP) and
trimesoyl chloride (TMC) solutions. The process involved fabrication of J
TFN membrane on the support membrane with amino and carboxyl A= (2)
ΔP
functionalized CQDs as aqueous additives. The membrane substrate, )
namely PSf was initially immersed in ⁓5 ml aqueous solution con­
Where J is the water flux (ml2 h , V is the permeate volume (l), t is the
taining 2% (w/v) PIP together with 0.2 wt % of functionalized CQDs as
reported by previous study [32]. Then, the membrane was taken out to experimental time (h), Am is the membrane area (m2), A represents
)
discard the residual liquid before further process. The membrane sup­
permeability (m2 hl bar , and ΔP is the pressure difference (bar).
port was then dipped into ⁓5 ml organic solution containing n-heptane
with 0.15% (w/v) of TMC for about 2 min [31]. This would then form On the other hand, a bench conductivity meter was used to evaluate
the polyamide (PA) layer on the membrane by interfacial polymeriza­ the salt concentration in the feed and permeate solutions. The salt
tion. Lastly, the obtained TFN membrane was dried in the oven at 60 ◦ C rejection through the membrane was measured by using the following
for 15 min to allow further polymerization. The TFN membrane with equation (3):
non-functionalized CQDs, CCQDs and NCQDs were denoted as TFN ( )
Cp
(non-functionalized CQDs), TFN(CCQDs) and TFN(NCQDs), respec­ R(%) = 1 − × 100 (3)
Cf
tively. The preparation of thin film composite (TFC) membrane was

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N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

Fig. 2. (a, c, e) HRTEM images of non-functionalized CQDs, CCQDs and NCQDs with insets showing clearer dots; (b, d, f) the particle size distributions of non-
functionalized CQDs, CCQDs and NCQDs, respectively.

Fig. 3. (a) FTIR and (b) UV–Vis spectra of non-functionalized CQDs, CCQDs and NCQDs.

Where Cp and Cf are the concentrations of permeate and feed respec­
tively in ppm. The setup of membrane performance is shown in Fig. 1.
3. Results and discussion
3.1. Morphology of CQDs
Fig. 2 shows the morphology of non-functionalized CQDs, CCQDs
and NCQDs with their particle size distribution. CCQDs and NCQDs
exhibit almost uniform distribution of spherical shapes compared to the
non-functionalized CQDs, indicating the formation of carbon dots. This
is due to hydrothermal process that mainly consists of a few reactions
such as polymerization and carbonization [33]. Hence, more condensed
structure of carbon dots is formed when carboxyl and amino sources
were added during hydrothermal to allow for functionalization. In
addition, functionalization process assists in the formation of clearer
carbon dots because of hybridization of C–OH from ascorbic acid and

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N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

C–NH2 from EDA to the structure of CQDs with sp2 conjugated π do­
mains [34].
All CQDs synthesized in this work exhibit diameter less than 10 nm
that implies their zero dimensional properties, similar to the conven­
tional CQDs [35]. Non-functionalized CQDs have average diameter of
9.75 ± 0.33 nm. Whereas CCQDs and NCQDs have average particle
diameter of 3.89 ± 1.74 nm and 1.56 ± 0.22 nm, respectively, which is
significantly smaller than the non-functionalized CQDs. This is because
functionalization increases the electron density of CQDs, hence this
causes quantum confinement effect to increase, leading to wide band
gap between HOMO and LUMO in CQDs structure [16]. However,
CCQDs are found to have a larger average particle size compared to
NCQDs due to protonation of H+ ions to CQDs structure as they are in
acidic condition [21]. This observation shows that the synthesis condi­
tion of CQDs also affect the obtained particle size as desired in certain
applications.

3.2. Functional group on functionalized CQDs

Fig. 4. XRD of all CQDs. The FTIR analysis for the prepared samples is presented in Fig. 3(a),
where oxygen containing groups are present in CQDs samples. Both
CCQDs and NCQDs are shown to possess hydroxyl (O–H) group repre­
sented by broad peak at range 3000–3600 cm− 1 due to the hydrothermal
synthesis method [36]. The presence of stretching vibration of C– –O

Fig. 5. (a) XPS full spectra of C1s, N1s and O1s for all CQDs, (b–d) XPS high resolution C1s spectra of CCQDs, NCQDs and non-functionalized CQDs, respectively,
(e–g) XPS high resolution N1s spectra of CCQDs, NCQDs and non-functionalized CQDs, respectively.

5
N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

Table 2a observe the optical properties of the CQDs structure. The presence of
Elemental composition in CQDs samples. observable peak at around 240 nm is due to π − π* electronic transition
CQDs samples C (at. N (at. O (at. N/C O/C of sp2 domains of carbon core [38]. Apart from that, there are observable
%) %) %) (%) (%) shoulders in the visible region in the wavelength ranges of 380–750 nm.
Non-functionalized 59.92 1.59 28.01 3.19 42.09 However, both CCQDs and NCQDs exhibit different peak position due to
CQDs the synthesis condition. In Fig. 3(b), it is observed that NCQDs tend to
NCQDs 60.60 15.51 23.82 21.97 40.82 have peak towards blue shift region compared to CCQDs. This is because
CCQDs 76.33 1.92 34.85 2.52 45.66 smaller size of NCQDs implies the condition of having higher band gap
between HOMO and LUMO, hence the energy to overcome the force of
attraction in CQDs structure is higher [39].

3.4. XRD and XPS analyses of functionalized CQDs

Diffraction patterns of non-functionalized, carboxyl and amino

Fig. 6. PL spectra of all CQDs.
Fig. 7. FTIR spectra of fabricated membranes.
bond at 1640 cm− 1 can be observed in CCQDs due to the synthesis that
used ascorbic acid. The finding is similar to a study reported by Zhao
et al. [37] which stated that hydrophilic groups could stabilize the
carbon nanoparticles in aqueous solution and that hydrophilic reaction
could easily happen. In NCQDs, amine containing functional groups are
abundantly present such as N–H bending and N–H stretching at 1580
cm− 1 and 2800 cm− 1, respectively. In addition, C–N stretching bond can
be observed at 1340 cm− 1 that originated from EDA during CQDs
synthesis.
functionalized CQD were obtained from XRD analysis as shown in Fig. 4.
The peaks centered at 2θ = ̴ 22.7◦ are attributed to the (002) lattice
spacing of carbon-based materials which reflect the nature of graphitic
carbon [40]. This observation also relates to the highly disordered
structure of carbon [41]. The peaks for both functionalized CQDs are
narrow and sharp compared to the non-functionalized one due to the
presence of additional functional groups such as C–– O and N–H in CQDs
structure [40,41]. This observation also confirms the high crystallinity
of the nanoparticles. Apart from that, the peaks centered at 2θ = ̴ 23◦ can
also be attributed to the formation of amorphous nanoparticles due to
pre-treatment of rice husks during the synthesis process. This is because
the pre-treatment of rice husks using HCl can further prevent irregular
aggregates of particles as reported in a previous research [42].
X-Ray Photoelectron Spectroscopy (XPS) analysis was implemented
to determine the elemental analysis and related chemical bonding states
in CQDs. XPS spectra in Fig. 5(a) show the presence of three distinct
peaks at binding energy of 285.0, 400.0 and 532.0 eV which correspond
to C1s, N1s and O1s, respectively [42]. These peaks indicate the pres­
ence of carbon, nitrogen and oxygen elements in the CQDs. The peak
intensity of carbon element arises in carboxyl functionalized CQDs while
there are clearer peaks at around 400 eV that correspond to existence of
nitrogen element in amino functionalized CQDs. High resolution XPS
spectra of C1s in Fig. 5(b-d) that correspond to the carbon features in
CQDs are found to be at 285.0 and 288.0 eV which indicate the presence
of C–C and C– – O bonds, respectively [33].
Meanwhile, the N1s spectra of amino functionalized CQDs in Fig. 5
(e-g) which show pronounced peaks at 399.8 and 401.7 eV, indicate the
presence of nitrogen associated groups which are N–C and N–H bonds,
respectively [43]. There is no obvious changes in binding energy with
different functionalization agents, which might be due to consistent
hydrothermal temperature as shown in a study by Li et al. [44] for the
synthesis reaction at temperature below 200 ◦ C. The elemental analysis
in terms of atomic percentage is presented in Table 2a. It can be seen that
the carbon content in CQDs is higher when functionalization with
carboxyl groups increases, while nitrogen content shows significant
increment in amino functionalized CQDs compared to
non-functionalized CQDs. Oxygen element also shows higher percentage
for all CQDs and this proves that CQDs contain high amount of
oxygen-containing groups. The nitrogen content of less than 2% in the
non-functionalized CQDs and CCQDs may be ascribed to the compo­
nents of rice husks. This is because rice husks contain around
0.05–4.26% of nitrogen of their overall elemental composition [19].
Hence, the utilization of rice husks during hydrothermal leads to the
occurrence of nitrogen element in the CCQDs even in a very small
amount.
3.5. PL analysis of functionalized CQDs

Photoluminescence (PL) is one of the intrinsic properties of CQDs

3.3. UV–Vis analysis of functionalized CQDs regardless of their synthesis methods [32,33]. PL gives the information
about energy level transition and radiative recombination of electron
UV–Vis analysis was implemented for both functionalized CQDs to and holes [33]. PL characteristic of CQDs also signifies the energy

6
N.H. Zainal Abidin et al.
Fig. 8. FESEM characterizations of top and cross sectional surfaces for (a-f)PSf, (b-g)TFC, (c–h) TFN (non-functionalized CQDs), (d–i) TFN(CCQDs), and (e–j)
TFN(NCQDs).
absorbed and emitted as photons. In addition, PL emission is affected by
particle size in which smaller particles tend to emit fluorescence prop­
erties at shorter wavelength. This is due to the presence of narrower
band gap in the sample structure, hence electron density is higher
causing the energy in the carbon core to increase [45]. Fig. 6 shows PL
properties of the non-functionalized and functionalized CQDs. NCQDs
7
Polymer Testing 100 (2021) 107270
exhibit blue shift emission in which shorter emission wavelength is
favored. The alkaline condition contributes to deprotonation in NCQDs,
which enhance the PL intensity of NCQDs due to their tiny sizes. In
contrast, CCQDs favor red shift emission as the band gap decreases, thus
less energy is required to overcome the force of attraction in CQDs
sample. This is because acidic environment enhances the protonation to
N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

Fig. 9. AFM 3D images of (a)PSf, (b)TFC, (c) TFN(non-functionalized CQDs), (d) TFN(CCQDs), and (e) TFN(NCQDs).

the O–H peak, further confirming their presence within the membrane.
Table 2b
Roughness of membranes: Ra (average roughness) and Rrms (root mean square
roughness). 3.7. Morphology of membrane
Membrane Ra Rrms
Morphology of fabricated membranes can be analyzed using FESEM
PSf 2.088 3.704 characterization as shown in Fig. 8. Both top and cross-sectional surfaces
TFC 2.512 4.361
TFN (Non-functionalized CQDs) 5.915 8.462
are presented for PSf support, TFC and all TFN membranes. In Fig. 8(a-
TFN (CCQDs) 2.295 3.739 e), PSf support shows relatively smooth surface while TFC and TFN
TFN (NCQDs) 5.874 8.322 membranes exhibit nodular structure with molecular globules, which
are similar to the typical structure of PA layer obtained through inter­
facial polymerization method between PIP and TMC [6] for cross
the negatively charged CQDs, hence larger particle size is expected from
sectional morphology in Fig. 8(e-h). PSf substrate shows large void due
CCQDs. Non-functionalized CQDs also exhibit broader red-shifted peak
to properties of the polymer. This morphological observation is due to
due to the particle size is significantly larger than the functionalized
faster solvent and non-solvent exchange rate during fabrication of PSf
CQDs.
support through phase inversion method [37]. There are appearances of
dense and thin films on the porous PSf substrates (shown by red-lined
3.6. Functional groups in membrane boxes) which indicate the formation of PA layer available for water
transport and less resistance for membrane during permeation test [32].
Functional groups in different membrane samples namely PSf sup­ The membranes exhibit PA layer with thickness ranges from 150 to 178
port, TFC and CDQs-containing TFN were analyzed using FTIR (Fig. 7). nm. This denser part represents the PA layer since it suits the typical
For all membrane samples, the peaks at specific wave numbers of 1150
cm− 1 and 1300 cm− 1 represent symmetric O– – S–– O stretching and
Table 3
asymmetric O– – S–
– O stretching, respectively, corresponding to the PSf
Contact angle measurement of membranes.
substrate [46,47]. The fabrication of PA layer (TFC) shows a charac­
Membrane Contact angle (◦ )
teristic peak at around 3416 cm− 1 represents O–H group while C– –O
bond can be observed at 1620 cm− 1, indicating the successful formation PSf 71.20
TFC 51.25
of PA layer [6]. Furthermore, peaks at 1364 cm− 1 for all TFN mem­ TFN (Non-functionalized CQDs) 32.34
branes that correspond to C–N stretching vibration also indicate the TFN (CCQDs) 23.67
presence of PA layer which was formed through interfacial polymeri­ TFN (NCQDs) 26.54
zation process [17,36]. The presence of functionalized CQDs intensified

Fig. 10. Contact angle illustrations of (a)PSf, (b)TFC, (c) TFN((Non-functionalized CQDs), (d) TFN(CCQDs), and (e) TFN(NCQDs).

8
N.H. Zainal Abidin et al. Polymer Testing 100 (2021) 107270

Fig. 11. Zeta potential of membrane samples.

Fig. 14. Salt rejection of membrane samples.

observation of PA layer formation on the membrane substrate. PA layer

is a thin and denser part on top of the membrane substrate which is the
PSf [40].
On the other hand, all TFN membranes display much rougher surface
compared to TFC due to the presence of CQDs nanoparticles. The
incorporation of CQDs contributes to the formation of ridge-and-valley
structure, which is a typical TFN membrane characteristics [35,38].
However, TFN incorporated with CCQDs does not show significant
ridge-and-valley structure due to higher electronegativity of the nano­
particles compared to the TFN with NCQDs as suggested by Sun et al.
[17]. Hence, this enhances the force of attraction between negatively
charged CCQDs with the PIP solution as aqueous phase and promotes
better dispersion within membrane. The reaction then results in lower
cross linking of aqueous phase containing PIP and organic phase con­
taining TMC during interfacial polymerization.

3.8. AFM analysis of membrane

Fig. 12. Pore size distribution of membrane samples. The surface roughness of membranes can be measured by AFM
analysis with their three-dimensional images as shown in Fig. 9 and
summarized in Table 2b. The nodular and valley surface of PSf substrate
is typical for membrane prepared using phase inversion method [31].
The presence of PA layer for TFC results in rougher surface, contributed
by the formation of granular structures on the top surface of the poly­
amide layer [48]. The presence of CQDs as nanofiller leads to formation
of rougher surfaces due to the interaction between the nanoparticles and
polyamide matrix [39,40]. A distribution of valley and peak type
morphology can be observed for all modified membranes as shown by
the dark and bright regions, respectively. However, it is observed that
TFN membrane with carboxyl functionalized CQDs exhibits smoother
surface compared to the TFN membrane with amino functionalized
CQDs due to the interaction between anionic CCQDs with amino groups
of PIP in aqueous phase during IP process [6]. The observation is also
consistent to the FESEM results. The interaction between CCQDs and PIP
causes the formation of less cross-linked polyamide layer due to hin­
dered reaction between aqueous and organic phases and consequently
leads to higher water permeability [49]. The observation is also related
to the hydrogen bonding occurred between aqueous phase and the
nanoparticles [48]. On the other hand, the presence of amino CQDs in
polyamide layer causes the PIP to have greater resistance for diffusion
Fig. 13. Permeate flux of membrane samples.
across the interface due to the electrostatic repulsion between cationic
groups in both NCQDs and PIP. Hence, more cross-linked structure of
polyamide layer is formed between aqueous and organic phases [17,37].
The roughness parameters of each membrane can be seen in Table 2b.

9
N.H. Zainal Abidin et al.
Fig. 15. (a, b) Flux and salt rejection of TFN (CCQDs) and (c, d) Flux and salt rejection of TFN (NCQDs).
3.9. Contact angle and zeta potential measurements
Fig. 10(a-e) show the variation in contact angle on PSf, TFC and TFN
upon addition of CQDs as nanofiller in PA layer. As can be seen, hy­
drophilicity of membrane was further enhanced upon incorporation of
functionalized CQDs compared to the pristine PSf and TFC. The contact
angle of membrane decreases in the order of PSf > TFC > TFN (non-
functionalized CQDs) > TFN (NCQDs) > TFN (CCQDs) which indicates
that hydrophilic properties of TFN is improved due to the presence of
hydrophilic carbon nanoparticles [17,35]. The presence of
oxygen-containing groups in CQDs assists in hydrogen bonding, hence
flux enhancement can be achieved. In addition, hydrophilicity corre­
sponds to the wettability of the membrane surface [49]. Lower contact
angle value gives the information about the dominance of adhesive force
between water molecules and membrane surface compared to cohesive
force between water molecules themselves [50]. However, in TFN
containing CCQDs shows much lower contact angle compared to other
TFN membranes due to higher electronegativity of carboxyl group
originated from the precursor during the synthesis process. This finding
is similar to a study by Sun and Wu [6] where TFN with carboxyl
functionalized CQDs exhibited more hydrophilic membrane for nano­
filtration. However, in that study, TFN incorporated with different types
of CQDs did not show any significant difference in terms of their hy­
drophilicity [17]. Table 3 shows the contact angle value of the mem­
brane samples.
On the other hand, zeta potential as can be shown in Fig. 11 indicates
that TFN incorporated with different CQDs either carboxyl or amino
functionalized CQDs exhibit more negatively charged surface compared
to TFC and PSf. This phenomenon can be attributed to the presence of
carboxyl and amino groups in the CQDs [51]. Hence, considering the
negatively charged chloride and sulphate ions in feed solution, this
would accelerate the electrostatic repulsion between solute particles and
the membrane surface. This will then lead to higher rejection during
nanofiltration process. In addition, the enhancement of negative charges
10
Polymer Testing 100 (2021) 107270
of TFN surfaces can easily attract water particles through hydrogen
bonding, thus leads to flux improvement. This observation also relates to
excellent antifouling properties of the fabricated TFN membranes [13].
3.10. Pore distribution of membrane
The pore size distribution is shown Fig. 12. PSf substrate exhibits the
largest pore diameter of around 0.2–0.25 nm with distribution of
15–20%. In addition, the PSf is porous resulting from the addition of PVP
as a pore former during the membrane fabrication [52]. The pore
diameter decreases when TFC is fabricated due to the presence of PA
layer on top of the PSf substrate. However, it further decreases when the
TFN membrane was incorporated with CQDs due to the tiny sizes of the
nanoparticles. The observation was in line with the morphological
analysis whereby the presence of CQDs could be detected in the PA layer
of the membrane substrate.
3.11. Performance of membrane
Fig. 13 shows the flux obtained from the fabricated membranes in
nanofiltration performance. It can be seen that the pure water and salt
solution flux are higher in TFN membranes compared to the pristine TFC
and PSf support. This observation can be attributed to the presence of
CQDs in the PA layer of the membranes. The presence of CQDs drives the
water transport through the active layer of PA structure and they assist
in enhancing the hydrophilicity of the membranes. This is also in
agreement with the contact angle measurement as the TFN membranes
exhibit lower contact angle compared to the PSf and TFC. The incor­
poration of carbon nanoparticles is ascribed to the introduction of a
medium for water molecules transport and provide frictionless surface
to facilitate the flow of water through the membrane matrix [6]. The
quantum size of the CQDs assists in excellent dispersion of the nano­
fillers in PA layer during membrane fabrication [53]. In addition, the
hydrogen bonding between water molecules and the negatively-charged
N.H. Zainal Abidin et al.
Table 4
Selected studies on CQDs incorporation in membrane.
Polymer Application Observation
PAN NF • Flux improvement varying from 50% to 6.8
times
PSf RO • Enhancement of water flux (20–32 L/m2 h)
and salt rejection (60–93%)
• The incorporation of carbon dots resulted in
higher chlorine resistance in membrane
PES NF • Membrane maintained high rejection of
Congo red of 99.8% and methylene blue of
97.6%
• The pure water flux achieved 23.33 L/m2 h
which was 1.5 times compared to the
pristine membrane
PAN FO • The introduction of carbon dots increases
the average diameter of the composite
nanofiber
PES NF • Enhanced antifouling resistance
• Larger carbon dots loading on membrane
surface could be observed under
fluorescence microscopy due to its
fluorescence properties
PES FO • Carbon dots with larger surface area and
abundant of ionic species favor high
osmotic pressure
• Higher water flux by increment of 55%
• Negligible reverse flux of draw solutes
PSf NF • Enhanced the hydrophilicity
• Incorporation of carbon dots causes more
water channels formed in the polyamide
layer
• The water flux was 6.8 times higher than
the pristine membrane
• The retention of Congo red and Orange GII
remained above 96% and 80% respectively
PSf NF • Thin film nanocomposite membrane has
smoother surface area and lower contact
angle
• Increased hydrophilicity for antifouling
properties
PSf NF • The flux could be achieved beyond 30 L/m2
h for TFN membranes with both carboxyl
and amino functionalized CQDs
• Salt rejection could be maintained above
90% for TFN with non-functionalized and
functionalized CQDs. No agglomeration
was observed during membrane fabrication.
PA layer of the membranes provides additional driving force for water to
be transported through the membranes [53].
The presence of oxygen-containing functional groups in both
carboxyl and amino functionalized CQDs gives a great impact in the
performance of TFN membranes in nanofiltration. However, an incre­
ment of around 23% of flux is observed for TFN with carboxyl func­
tionalized CQDs compared to the one with amino CQDs. This can be
attributed to the higher electronegativity of CCQDs that produces highly
negative charged PA layer to allow more hydrogen bonding with water
molecules. This observation is also closely related to the membrane
hydrophilicity due to the introduction of non-functionalized and func­
tionalized CQDs. However, TFN with amino functionalized CQDs ex­
hibits slightly lower permeability compared to TFN with carboxyl CQDs.
This is because the incorporation of amino groups create a denser PA
layer due to possible reaction between amine solution and TMC, hence
limiting the water transport through the membrane [6].
On the other hand, the performance of the fabricated membranes in
salt rejection at pressure of 6 bar are observed to explore their capa­
bilities in reducing solute concentration in the permeate. As shown in
Fig. 14, TFC and all TFN membranes can reject higher salts compared to
the PSf. More than 90% of salts are rejected in TFC and TFN membranes,
significantly higher than PSf which can only reject less than 50% of salts.
The rejection follows the trend of TFC > TFN (CCQDs) > TFN (NCQDs)
Polymer Testing 100 (2021) 107270
> TFN (CQDs) > PSf. It can be observed that TFC has the highest
rejection due to the highly cross-linked structure obtained from inter­
Ref. facial polymerization of PIP and TMC. However, the rejection of Na3PO4
for all membranes is higher compared to the NaCl. The ability of the TFN
[57]
membranes in salt rejection is ascribed to the highly negative charged
[58] PA layer, hence creating a stronger electrostatic repulsion of the chloride
and phosphate anions with the active PA layer. The negatively charged
membrane can attract high valent cations and repel monovalent and
[59]
high valent anions.
However, in comparison of all salts, the rejection of CuSO4 is the
highest compared to the others, due to the effect of hydrated radius of
the anion. The rejection follows the trend of CuSO4 > Na3PO4 > MgCl2
> CaCl2 > NaCl. SO24 ‾, PO34 ‾ and Cl ‾ ions have hydrated radii of 0.412,
[55] 0.340 and 0.332 nm, respectively, thus indicating that sulphate is larger
than the chloride ions [54]. This also corresponds to the Donnan effect
that is usually affiliated in nanofiltration. The negatively charged PA
[60] layer formed through interfacial polymerization between PIP and TMC
tends to repel multivalent anion (SO24 ‾ and PO34 ‾) compared to
monovalent anion (Cl ‾). This explains the higher rejection of CuSO4 and
Na3PO4 compared to NaCl. Hence, the electrostatic repulsion is strong
[61] enough to hold back the sulphate and phosphate anions, leaving them in
the retention part. The recyclability of both TFN (CCQDs) and TFN
(NCQDs) are shown in Fig. 15. It can be seen that the flux and salt
rejection slightly decrease on the second run of experiment for both
[62] membranes, however they could be maintained after the third run. This
observation may be attributed to the hydrophilic nature of the CQDs to
assist in water transport. The trends decline after sometimes due to
possible solute deposition on the membrane active layer as well as
smaller size of membrane used in the setup which has a diameter of
around 4.1 cm only.
[63]
3.12. Comparison with previous studies
A study by Zhao et al. [55] stated that CQDs incorporated membrane
with PSf substrate exhibited enhanced permeability compared to the
This
work
pristine membrane due to its hydrophilicity. On the other hand, He et al.
[56] investigated on the effect of sodium functionalized CQDs
embedded in TFN membrane for arsenic and selenium removal. The
study reported that membrane incorporated with 0.05 wt% of sodium
functionalized CQDs resulted in water flux of 53.54 L/m2 h which was
higher than the non-modified membrane. Furthermore, the presence of
sodium and oxygen-containing groups in the membrane structure led to
more hydrophilic condition for water treatment application. Numerous
studies have been made to observe the effect of CQDs in membrane as
presented in Table 4.
4. Conclusions
This work reports the fabrication of TFC and TFN membranes with
the incorporation of CQDs. Thin polyamide (PA) layer incorporated with
non–functionalized and functionalized CQDs were formed on poly­
sulfone (PSf) membrane support through interfacial polymerization
method between aqueous and organic phases. Zeta potential measure­
ment shows that TFN incorporated with different CQDs either carboxyl
or amino functionalized CQDs exhibit more negatively charged surface
compared to TFC and PSf. This phenomenon can be attributed to the
presence of carboxyl and amino groups in the CQDs. AFM analysis shows
that the presence of CQDs as nanofiller leads to the formation of rougher
surfaces due to the interaction between the nanoparticles and polyamide
matrix. In addition, the appearance of photoluminescence peak intensity
for each TFN membrane shows that CQDs are small enough to be
embedded in the PA layer as shown in PL analysis. All TFN membranes
show higher flux and permeability compared to TFC due to enhanced
hydrophilicity. More than 90% salts rejection are also achieved for TFN
membranes due to their highly negative charged PA layer. The recy­
clability of TFN membranes with both carboxyl and amino
11
N.H. Zainal Abidin et al.
functionalized CQDs were tested for three runs of experiment. There­
fore, this study suggests that the presence of functionalized CQDs in
polyamide layer of membrane could tune the properties of the fabricated
membrane with potential application in nanofiltration.
CRediT authorship contribution statement
Nur Hafizah Zainal Abidin: Writing – original draft, Writing – re­
view & editing, Methodology, Investigation. Siti Nur Alwanie Shafie:
Investigation, Methodology. Hazwani Suhaimi: Writing – review &
editing. Nonni Soraya Sambudi: Writing – review & editing, Supervi­
sion, Methodology, Resources, Funding acquisition. Nik Abdul Hadi
Sapiaa Md Nordin: Writing – review & editing, Methodology,
Supervision.
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.
Acknowledgements
This work was supported by Ministry of Higher Education Malaysia
(MOHE) under Fundamental Research Grant Scheme (FRGS/1/2018/
TK02/UTP/03/3) and YUTP FRG (015 LC0-211).
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