Journal of Membrane Science 679 (2023) 121706

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Journal of Membrane Science

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

Smart integration of MOFs and CQDs to fabricate defect-free and

self-cleaning TFN membranes for dye removal
Die Ling Zhao a, Haiyi Jin a, Qipeng Zhao b, Yanchao Xu a, Liguo Shen a, Hongjun Lin a, **,
Tai-Shung Chung b, c, *
a
College of Geography and Environmental Sciences, Zhejiang Normal University, Jinhua, 321004, China
b
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore
c
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, 10607, Taiwan

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

Keywords: The surface chemistry and functionality of metal-organic frameworks (MOFs) can be manipulated through a
Metal-organic frameworks judicious choice of integration with other nanomaterials. In this work, heterojunctions of UiO-66-NH2 and
Carbon quantum dots carbon quantum dots (CQDs) were prepared to explore their synergetic advantages as nanofillers in thin-film
Thin-film nanocomposite
nanocomposite (TFN) membranes for dye removal. The successful integration of UiO-66-NH2/CQD were veri­
Nanofiltration
fied by TEM, FT-IR and XPS. The uniform loading of ultra-small CQDs on the surfaces of UiO-66-NH2 can not only
Self-cleaning
Dye removal enhance their compatibility with the polyamide matrix, but also promote their photocatalytic oxidation under
visible light. Therefore, comparing to the pristine thin-film composite membranes, the optimal TFN membranes
embedded with 0.2 wt% of UiO-66-NH2/CQD have demonstrated remarkable improvements in pure water
permeance by 89.7% and higher selectivity to dyes of different charges and molecular weights. In addition, the
decrease of water flux caused by dye adsorption during the long-term filtration process can be recovered by
92–99% via photocatalytic degradation of the attached dyes within 10 min. This work may offer a new strategy
for fabricating defect-free and self-cleaning nanofiltration membranes for dye removal and wastewater
reclamation.

1. Introduction accumulate, yielding a declined membrane permeability and separation

Treatment and recycle of industrial wastewater are of great impor­
tance given their severe menace to the environment and the growing
global water scarcity [1–5]. Among them, dye wastewater produced
from textile, dye production and printing industries has raised people’s
attention, while conventional treating methods (e.g., adsorption,
advanced oxidation or microbial degradation) still face challenges such
as low efficiency and poor feasibility in dye recycle [6,7]. In recent
years, nanofiltration (NF), which can effectively repel dye molecules
with relatively low molecular weights of <2000 Da, has emerged as a
competitive and desirable alternative due to its ability to remove and
recycle the dyes simultaneously [8–10]. Nevertheless, the current
dominant membranes for NF processes; namely, thin-film composite
(TFC) membranes are still limited by the “trade-off” relationship and
membrane fouling [11]. Especially in dye wastewater treatment, dye
molecules can anchor to the membrane surface and gradually
efficiency [12,13]. Therefore, it is imperative to develop NF membranes
with both high performance and self-cleaning ability for dye wastewater
treatment [14–18].
Metal-organic frameworks (MOFs) were intensively studied as
nanofillers in the selective layers [19–22]. With well-defined and highly
tunable nano-sized channels, MOFs are able to sieve solutes larger than
the channel but allow molecules with smaller sizes to traverse, rendering
them great feasibility of applications in the fields of gas and liquid
separation [23–26]. Additionally, benefitting from their relatively rigid
crystalline nature, MOFs can surpass organic porous species, such as
covalent-organic frameworks (COFs) and polymers of intrinsic micro­
porosity (PIMs), which are plagued by aging and reduction of porosity
[27]. On the other hand, inorganic porous nanomaterials like zeolites
are suffering from less diversity in chemistry and structure, as well as
lower processability [28]. Therefore, featuring with relatively robust
pore structure, rich tunability and good processability, MOFs have

* Corresponding author. Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore.
** Corresponding author.
E-mail addresses: hjlin@zjnu.cn (H. Lin), chencts@nus.edu.sg (T.-S. Chung).

https://doi.org/10.1016/j.memsci.2023.121706
Received 19 January 2023; Received in revised form 20 April 2023; Accepted 29 April 2023
Available online 5 May 2023
0376-7388/© 2023 Elsevier B.V. All rights reserved.
D.L. Zhao et al.
Fig. 1. Diagram to prepare UiO-66-NH2/CQD and TFN membranes.
attracted fast growing research interests as nanofillers [19,29–35].
However, because of their partial inorganic property from the metal
centers and propensity to agglomerate at a high loading, the in­
compatibility between MOFs and the polyamide matrix tends to form
peripheral macrovoids around MOFs and results in a defective selective
layer [19,36]. Meanwhile, although some MOFs like UiO-66-NH2 can act
as photocatalysts to generate reactive oxygen species (ROS), their cat­
alytic activity is restrained by their insufficient active sites, rapid
recombination of photo-induced charges and unsatisfied visible light
absorption [37–41].
Herein, heterojunctions prepared by functionalizing UiO-66-NH2
with ultrafine carbon quantum dots (CQDs, 2− 3 nm) via covalent
bonding between amine groups of UiO-66-NH2 and carboxyl groups of
CQDs were investigated as novel nanofillers in thin-film nanocomposite
(TFN) NF membranes (Fig. 1). It is believed that the carbonaceous and
hydrophilic CQDs could not only facilitate the nanofiller dispersion and
improve their compatibility in the selective layer but also enhance the
photocatalytic property to absorb visible light and suppress recombi­
nation of photoinduced electrons/holes [42–44]. Experimental results
from this work have confirmed our hypothesis. The UiO-66-NH2 nano­
particles anchored with CQDs not only endowed the TFN membranes
with higher permselectivity against dyes but also improved the water
permeance from 12.4 to 23.5 L m− 2 h− 1 bar− 1. Furthermore, superior
photocatalytic self-cleaning ability has been demonstrated by a high
recovery rate (92-99%) of water flux after visible light irradiation for
only 10 min. This type of novel TFN membranes may have tremendous
potentials in practical wastewater treatment and purification due to the
combination of outstanding separation efficiency and excellent
self-cleaning functionality.
2. Materials and methods
2.1. Materials
2-aminoterephthalic acid (ATA, >98%, Shanghai Aladdin Biochem­
ical Technology), acetic acid (AA, Sinopharm Chemical Reagent), 1,3,5-
bezeneetricarbonyl trichloride (TMC, 98%, Alfa Aesar), citric acid
(>99.5%, Shanghai Aladdin Biochemical Technology), N-(3-dimethy­
laminopropyl)-N′ -ethylcarbodiimide hydrochloride (EDC, 98.5%,
Shanghai Macklin Biochemical), piperazine (PIP, >98%, TCI Shanghai),
hexanes (≥97%, Chengdu Kelong Chemical), dimethylformamide (DMF,
≥99.5%, Tianjin Kermel Chemical Reagent), zirconium chloride (ZrCl4,
98%, Meryer (Shanghai) Chemical Technology), N-hydroxysuccinimide
(NHS, 98%, Shanghai Macklin Biochemical), sodium chloride (NaCl,
≥99.5%, Shanghai Lianshi Chemical Reagent), sodium sulfate (Na2SO4,
2
Journal of Membrane Science 679 (2023) 121706
≥99%, Sinopharm Chemical Reagent), methyl blue (MB, 98%, Bide
Pharmatech), methylene blue (MLB, Sinopharm Chemical Reagent),
methyl orange (MO, Shanghai Zhanyun Chemical), and direct red 23
(DR23, Heowns Biochem Technologies) were all used without any pre­
treatment. Polyvinylidene difluoride (PVDF) supports were provided by
Da Fu Membrane Technology Co., Ltd. (Jiangsu, China). Deionized (DI)
water (resistivity: 15 MΩ cm) was obtained from a Milli-Q integral unit
(Millipore).
2.2. Preparation and characterizations of UiO-66-NH2/CQD
UiO-66-NH2 were prepared via a solvothermal process [30,45]. ZrCl4
(0.32 g) was first dissolved in 160 mL DMF and ultrasonicated for 30
min. Then 0.25 g of ATA and 1.2 mL of AA were added in the solution,
followed by carrying out the reaction in an oven at 100 ◦ C for 18 h.
Afterwards, the solution was centrifuged at 8000 rpm, washed by DMF
and dried at 60 ◦ C. To synthesize CQDs, citric acid powders were grinded
and then put in a glass container. After being heated at 180 ◦ C for 3 h,
the white powder turned into yellow solids [46]. Then the solids were
dissolved in water and purified with a dialysis membrane (2K MWCO),
followed by being freeze dried to get CQD powders. Finally, CQDs (0.2
wt%) were applied to a UiO-66-NH2 aqueous solution (0.1 wt%) and
magnetically stirred for 24 h to integrate UiO-66-NH2 with CQDs, with
the presence of EDC/NHS (0.1 and 0.3 wt%, respectively). The solution
was centrifuged at 8,000 rpm and washed by DI water for several times
to remove excessive CQDs and EDC/NHS.
Transmission electron microscopy (TEM) images of nanoparticles
were examined by a JEM-2100F electron microscope (accelerating
voltage: 200 kV). X-ray photoelectron spectroscopy (XPS) character­
izations were analyzed by an Escalab 250Xi with a monochromatized Al
cathode (1486.71 eV photons) used as the X-ray source. Core-level
spectra were retrieved with a photoelectron take-off angle of 90◦ (α,
relative to the sample surface). All binding energy peaks were calibrated
according to the reference of neutral C 1s hydrocarbon peak at 284.6 eV.
The X-ray diffraction (XRD) patterns were obtained by an X-ray
diffractometer (Bruker D8 ADVANCE) with Cu K-α (λ = 0.154 nm) as the
radiation source. Their surface area and porosity were determined via a
Nova 400E by the Brunauer-Emmett-Teller (BET) method. Functional
groups were investigated utilizing a Fourier transform infrared (FT-IR)
spectroscopy (Nexus 670) with the scanning wavelength ranging from
400 to 4000 cm− 1.
2.3. Preparation and characterizations of membranes
The pristine TFC NF membranes were fabricated by interfacial
D.L. Zhao et al.
Fig. 2. TEM images of (a) UiO-66-NH2 (b) CQDs and (c) UiO-66-NH2/CQD; and their (d) FT-IR, (e) XRD spectra, and (f) nitrogen adsorption/desorption isotherms of
UiO-66-NH2 and their CQD composites.
polymerization of PIP and TMC as reported previously [47]. Firstly, a
piece of PVDF substrate was rinsed in water (containing 0.2 wt% PIP) for
2 min, which was then placed on a tissue paper until the surface was
clear of water droplet. Afterwards, it was dip-coated in hexane con­
taining 0.15 wt% TMC for 1 min. Finally, the thus formed TFC mem­
brane further cured at 60 ◦ C in oven for 5 min and stored in DI water for
characterizations and performance evaluation.
Similarly, TFN membranes were fabricated by the above-mentioned
procedures except pre-mixing the nanoparticles (0.05, 0.1, and 0.2 wt%)
in the PIP solution. The resultant membranes were named as TFN-M (i.
e., pre-mixing with UiO-66-NH2) or TFN-MC (i.e., pre-mixing with UiO-
66-NH2/CQD), and the following numbers 1, 2, and 3 indicate the
nanoparticle concentrations in PIP solutions of 0.05, 0.1, and 0.2 wt%,
respectively. For example, TFN-MC3 is dosed with 0.2 wt% UiO-66-
NH2/CQD.
The morphologies of membranes were analyzed by a field emission
scanning electron microscope (FESEM, GeminiSEM 300). Atomic force
microscopy (AFM, Bruker Dimension Icon) analyzed the surface
microstructure and quantitatively determined their average mean
roughness (Ra) and root mean square roughness (Rq) with a scanning
area of 10 × 10 μm2 at 10 different places via the tapping mode in air.
The water contact angles along time were recorded by a goniometer
(Biolin Scientific Attention Theta Flow). Surface charges were analyzed
by a zeta potential analyzer (Zeta 90 Plus).
2.4. Evaluation of NF performance
Pure water permeance (PWP, L m− 2 h− 1 bar− 1) and rejections to
Na2SO4 and dyes (R, %) of membranes were tested using a dead-end
filtration device at 5 bar while the membrane area was 12.6 cm2. It
was equipped with a magnetic stirrer, a digital balance and a pressurized
N2 cylinder. In each test, the data was collected after the membrane was
stabilized for 30 min. PWP was calculated according to equation (1) as
below:
PWP = ΔV/(Am × Δt × ΔP) (1)
where ΔV (L) represents the permeate volume through the filtration area
Am (m2) during the test duration Δt (h) under a trans-membrane pressure
difference of ΔP (bar).
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Journal of Membrane Science 679 (2023) 121706
Na2SO4 (1000 ppm) and four representative dyes (i.e., MLB, MO,
DR23 and MB, 5–30 mg/L) were employed to evaluate the membrane
selectivity. The rejection (R, %) was calculated using the equation
below:
R = 100% × (1− Cp/Cf) (2)
where Cp and Cf are the concentrations of salts or dyes in the respective
permeate and feed solutions. The Na2SO4 concentration was determined
according to the conductivity tested on a conductivity meter (Precision
Scientific Instrument, Rex DDS-307A), while for the dyes, a UV–vis
spectrophotometer (Yipu Instrument, TU-1810) was adopted to measure
their concentrations.
2.5. Photocatalytic activity and self-cleaning performance evaluation
Characterizations of photocatalytic ability of UiO-66-NH2 prior and
after the CQD integration were conducted. Their ability to harvest
visible light were investigated and compared by UV–vis diffusion
reflectance spectra (DRS, Agilent Cary 5000). Additionally, the electron
spin resonance (ESR) spectra of DMPO-•OH and DMPO-•O−2 were
recorded on a Bruker A300 spectrometer. The self-cleaning ability of
membranes after the addition of UiO-66-NH2/CQD was evaluated using
MB as the model foulant. The flux change and rejection to MB were
monitored along the time. After each cycle of 5 h, the membrane was
exposed to the visible light (provided by a 300 W Xenon lamp equipped
with a UV-cut filter) for 10 min. After simple rinse by DI water, the
membrane was placed back in the filtration device and continuously
tested for 0.5 h to determine its pure water permeance and recovery rate.
Ten cycles were performed for each membrane sample.
3. Results and discussion
3.1. Characterizations of UiO-66-NH2/CQD
Fig. 2(a–c) show the TEM images of UiO-66-NH2, CQDs and UiO-66-
NH2/CQD nanoparticles. After immobilization of ultrafine CQDs
(average size: 2–3 nm) on the UiO-66-NH2, one can see that black dots
are uniformly dispersed on the MOF surface (Fig. 2c). The FT-IR spectra
shown in Fig. 2d indicate that characteristic peaks for –NH2 of UiO-66-
D.L. Zhao et al. Journal of Membrane Science 679 (2023) 121706

Fig. 3. XPS spectra of UiO-66-NH2, CQDs and UiO-66-NH2/CQD.

Fig. 4. SEM (both topology and cross-section) and AFM images of membranes.

4
D.L. Zhao et al.
Fig. 5. (a) Contact angles, (b) zeta-potential, and (c) PWP and rejections to NaCl and Na2SO4 of membranes.
NH2 (1050 and 3452 cm− 1) almost disappear in the spectra of UiO-66-
NH2/CQD as they have reacted with CQDs. Meanwhile, a shoulder peak
at 1685 cm− 1 for –C– – O bond appears due to the introduction of CQDs
which are rich in these groups. XPS results also validate the existence of
–COOH on the CQD surface and their successful covalent immobilization
on the MOF surface (Fig. 3). The high intensity of the O–C– – O peak in
CQDs’ C 1s core-level spectrum implies rich carboxyl groups on the
surface [46]. Although part of them reacted with –NH2, the leftovers still
endow the UiO-66-NH2/CQD with a higher O–C– – O peak. In addition,
the total intensity of N 1s peak in UiO-66-NH2/CQD is weakened by the
coverage of CQDs which have no N element. As part of –NH2 has reacted
with –COOH, and part of N–H has turned into C–N, the ratio between
N–H and C–N peaks in the N 1s spectrum of UiO-66-NH2/CQD is lower
than UiO-66-NH2. All these data confirm that CQDs are successfully
anchored on UiO-66-NH2.
The crystallinity of UiO-66-NH2 and their CQD nanocomposites by
XRD were shown in Fig. 2e. All characteristic diffraction peaks of UiO-
66-NH2 are well in line with the simulated ones. The peaks at 7.3, 8.4
and 25.6◦ are from the respective (111), (002) and (006) planes [30,45].
The perfectly fitted peaks between the pristine UiO-66-NH2 and the CQD
integrated ones indicate that the CQD addition has negligible influence
on the crystal structure of UiO-66-NH2. Fig. 2f displays the N2 adsorp­
tion/desorption isotherms. The pristine UiO-66-NH2 exhibit a large
surface area of 457.9 m2/g and a N2 adsorption capacity of 740 cm3/g
STP. After the CQD addition, the surface area increases to 610.8 m2/g
while the N2 adsorption capacity drops to 550 cm3/g STP. It is specu­
lated that the increment in surface area results from the surface-grafted
CQDs. However, CQDs could also possibly block partial pores of
UiO-66-NH2, thus reducing the N2 adsorption.
3.2. Characterizations of membranes
Fig. 4 illustrates the membrane morphology by both SEM and AFM.
The TFC membrane exhibits a relatively smooth top surface with a low
surface roughness (i.e., Ra: 18.7 ± 2.1 nm, Rq: 24.6 ± 3.5 nm) measured
by AFM. After dosing UiO-66-NH2, the membrane begins to show a
typical ridge-and-valley architecture which gives rise to the surface
roughness to Ra of 34.8 ± 3.9 nm and Rq of 44.8 ± 5.6 nm. As illustrated
by a previous study, the difference in roughness results from the
5
Journal of Membrane Science 679 (2023) 121706
confinement effect because the MOF interlayer would prevent the
degassed nanobubbles from escape during the interfacial polymeriza­
tion, this would lead to form a thinner but larger polyamide leaves with
such a ridge-and-valley structure [48]. When embedding
UiO-66-NH2/CQD, the resultant TFN membrane possesses a leaf-like
polyamide. However, its surface roughness is lower (i.e., Ra: 23.4 ±
5.7 nm, Rq: 32.1 ± 7.8 nm) than TFN-M3 possibly due to better affinity
between UiO-66-NH2/CQD and PIP that decelerates the PIP diffusion for
interfacial polymerization [45]. Both nanofillers can be easily observed
from the cross-sections of their polyamide layers.
Surface wetting behavior of membranes were indicated by the water
contact angles (Fig. 5a). The TFC, TFN-M3 and TFC-MC3 membranes
exhibit similar and relatively low water contact angles of around 69◦ at
the instant when the water droplet hits the membrane surfaces. How­
ever, the variations of the measured contact angles with time are slower
for TFN-M3 and TFN-MC3 than TFC because the partial surface pores of
the former have been covered by the nanofillers with a rougher surface
than the latter. Fig. 5b displays the surface charges of the membranes.
The pristine TFC membrane is negatively charged, while the TFN-M3
membrane becomes less negative charged because of the incorpora­
tion of positively charged UiO-66-NH2 in the selective layer. However,
TFN-MC3 has a more negatively charged surface than TFN-M3 owing to
the attachment of the negatively charged CQDs on UiO-66-NH2
nanoparticles.
3.3. Filtration performance
The membrane filtration performance (i.e., PWP and R to Na2SO4) of
the TFC, TFN-M and TFN-MC membranes with different nanoparticle
loadings were compared in Fig. 5c. The pristine TFC membrane has a
satisfactory average PWP of 12.37 L m− 2 h− 1 bar− 1 and a Na2SO4
rejection of 99.3% at 5 bar. After adding 0.05 and 0.1 wt% UiO-66-NH2,
TFN-M1 and TFN-M2 membranes possess higher PWPs of 13.45 and
19.43 L m− 2 h− 1 bar− 1, respectively, due to the “gutter layer” effect
[49]. However, a drop in Na2SO4 rejection was also observed which may
arise from the agglomeration of nanoparticles. A further increase in
UiO-66-NH2 dosage to 0.2 wt% in PIP, the membrane permeability
drops due to the adverse influence of particle agglomeration. It increases
the membrane tortuosity and thus the resistance for water molecules to
D.L. Zhao et al. Journal of Membrane Science 679 (2023) 121706

Table 1
Dye rejections of the control TFC and TFN-MC3 membranes.
Dyes MLB MO DR23 MB

Molecular structure

Charge + – – +
Molecular weight 319.85 327.33 769.76 799.80
R of TFC 71.94 86.75 99.81 99.66
R of TFN-MC3 82.23 96.10 99.82 99.95

Fig. 6. Rejections and selectivity for (a) Na2SO4 and dye mixed solutions and (b) NaCl and dye mixed solutions of the TFN-MC3 membranes.

Fig. 7. (a) UV–vis DRS, and ESR spectra of (b) DMPO-•OH and (c) DMPO-•O−2 of UiO-66-NH2, CQD and UiO-66-NH2/CQD; (d) possible photodegradation mech­
anism of UiO-66-NH2/CQD under visible light.

6
D.L. Zhao et al.
Fig. 8. The normalized water fluxes and MB rejections of (a) TFC and (b) TFN-MC3 membranes as a function of time with photodegradation under visible light and
water wash after every 5 h for 10 cycles; the optical surface photographs of (c) TFC and (d) TFN-MC3 membranes before and after photodegradation and water wash.
traverse through. The growing agglomeration also reduces the Na2SO4
rejection to 92.5%. In contrast, with the aid of CQD deposition on
UiO-66-NH2, it prevents them from agglomeration and improves the
integrity of the selective layer. Consequently, the TFN-MC3 membrane
shows an enhanced PWP up to 23.46 L m− 2 h− 1 bar− 1 and an acceptable
R to Na2SO4 of 97.7%. The rejections to NaCl of membranes followed a
similar trend of R to Na2SO4.
Both the control TFC and TFN-MC3 membranes were also evaluated
for dye removal using four commercially available dyes. Table 1 pro­
vides the details of these dyes (i.e., charge, molecular weight, and
chemical structure). Comparing to the TFC membrane, TFN-MC3 ex­
hibits higher rejections to all the dyes. Obviously, the addition of
molecule-sieving UiO-66-NH2/CQD endows the resultant membrane
with additional size-sieving capability. In particular, even for dyes with
relatively lower molecular weights like MLB and MO, TFN-MC3 can still
possess quite high rejections of 82.23 and 96.10%, respectively. The
higher MO rejection is partially because of the electrostatic repulsion as
the membrane is also negatively charged. While for dyes with higher
molecular weights (i.e., DR23 and MB), TFN-MC3 has their rejections up
to 99.82 and 99.66%, respectively, indicating its excellent molecular
sieving property. In short, the TFN-MC3 membrane exhibits noteworthy
enhancement in both membrane permeability and selectivity.
The separation performance for mixed solutions containing both
salts and dyes of the TFN-MC3 membranes were also investigated. As
shown in Fig. 6a, compared with sole dye solutions, with the presence of
Na2SO4, the rejections against MO and DR23 are lower. This is because
7
Journal of Membrane Science 679 (2023) 121706
the Na2SO4 would shield the electrostatic repulsion between the nega­
tively charged dye molecules (i.e., MO and DR23) and the membrane
surface. Due to the ionic interactions between Na2SO4 and these two
dyes, the transportation of Na2SO4 through the membranes were also
promoted, leading to a lower Na2SO4 rejection in these two cases. On the
contrary, also due to the change in charge properties of dye molecules,
the rejections towards the positively charged dyes (MLB and MB) in the
mixed solutions increased, together with a higher Na2SO4 rejection
because of their retarded transportation through the membranes [47].
The selectivity between dyes and Na2SO4 is not high since their
respective rejections of TFN-MC3 are both quite high. For the dye and
NaCl mixed solution, the rejection followed the same trend, while the
selectivity between dyes and NaCl are higher than those of Na2SO4/dye
mixtures especially for NaCl/MB (Fig. 6b).
3.4. Evaluation of self-cleaning performance
A UV–vis DRS analyzed the light absorption abilities of CQDs, UiO-
66-NH2, and their nanocomposites (Fig. 7a). UiO-66-NH2 has relatively
strong absorption only in the UV range (250–420 nm), consistent with
previous reports [50,51]. In contrast, CQDs show much stronger light
harvesting especially in the visible region (400− 700 nm). As a result,
after CQD decoration, the absorption edges of the constructed nano­
composites shifted to the longer wavelength with relative to
UiO-66-NH2 (Fig. 7a), implying a stronger response to visible light and
more electrons/holes formed.
D.L. Zhao et al.
Fig. 7b and c compare their ROS generation using a DMPO trapped
ESR technique. The signals of DMPO-•OH and DMPO-•O−2 in the ESR
spectra confirm the generation of both •OH and •O−2 under visible light
illumination. In addition, the UiO-66-NH2/CQD nanocomposites have
stronger signal intensities for both •OH and •O−2 than the UiO-66-NH2.
Interestingly, •OH shows a more increment in signal intensity than •O−2 ,
indicating CQD facilitates more generation of •OH. These results
strongly validate that the addition of CQDs can improve the utilization
efficiency of visible light to produce ROS for greater photocatalytic ef­
ficiency under visible light. Fig. 7d illustrates the possible photo­
degradation mechanism for dyes under visible light. When the energy of
the light is equal to or higher than the energy band gap (Eg) between the
valence band (VB) and the conduction band (CB), the electrons of UiO-
66-NH2/CQD nanocomposites can be excited from the VB to the reversal
band. Then, the electrons will combine with O2 and H2O to form •O−2
and •OH, which can degrade dyes into smaller molecules and even CO2
and H2O [52,53]. Additionally, the active radicals may inactivate mi­
croorganisms on the membrane, improving the antibacterial ability of
TFN membranes as hypothesized previously [54].
The self-cleaning ability of UiO-66-NH2/CQD embedded membranes
under visible light was studied using a MB solution. Fig. 8a and b
compares the evolution of normalized water fluxes and R to MB of the
TFC and TFN-MC3 along time with photocatalysis under visible light for
10 min during the step of membrane washing (i.e., cleaning). The
normalized water flux is the ratio of real-time water flux to the original
PWP after stabilization for 30 min. For the TFC membrane, the water
flux continuously declines to 82% in the first 5 h as MB molecules
accumulated on the membrane during the filtration process. After
photocatalysis and DI water washing (Fig. 8c), the water flux is recov­
ered to 90% due to water rinse, but it drops faster to 60% after filtrating
the MB solution for another 5 h. After 10 consecutive runs, the PWP is
only 72% of the original PWP, and water flux for dye wastewater
filtration ends with 57% of the original PWP.
For the TFN-MC3, the water flux declines to 82% in the first cycle as
well (Fig. 8b). After visible light illumination for 10 min and then water
washing, the water flux recovery rate of the TFN-MC3 is 99%, demon­
strating its excellent self-cleaning ability. The optical photographs of the
membrane surface (Fig. 8d) confirm our hypothesis. The dyes on
membrane surface have turned black due to photocatalytic degradation
and they can be easily washed away. The PWPs in the subsequent cycles
are all restored to >92% after the same procedure. It is noteworthy that
both TFC and TFN-MC membranes are robust. They have high and stable
MB rejections before and after 10 cycles of photodegradation and water
wash processes. The rejection to Na2SO4 after 10 cycles has also been
tested, which (97.93%) showed negligible difference to the original
value (97.78%). This implies that no damage of the membrane structure
was formed after multiple photocatalysis.
4. Conclusions
To conclude, novel photocatalytic self-cleaning NF membranes were
constructed by intercalating UiO-66-NH2/CQD nanocomposites into the
selective layer. The combination of UiO-66-NH2 and CQDs can not only
remarkably improve the pure water permeance by 89.7% but also in­
crease rejections to dyes with different molecular weights and charges.
In addition, CQDs enhance the visible light induced photocatalysis ac­
tivity of UiO-66-NH2 by increasing the absorption rate of visible light
and inhibiting recombination of photo-induced electrons/holes, facili­
tating the self-cleaning process of the membrane surface by fast photo­
catalytic degradation of foulants in 10 min. The water flux can be
recovered to 92− 99% of its initial state in the 10 runs of dye wastewater
filtration. In contrast, by the same procedure the PWP of TFC mem­
branes can only be recovered to 72% after 10 cycles. This work may
render useful opportunities for developing high-performance and self-
cleaning NF membranes to treat wastewater and reclaim clean water.
8
Journal of Membrane Science 679 (2023) 121706
Author statement
Die Ling Zhao: Methodology, Validation, Investigation, Writing-
Original Draft. Haiyi Jin: Validation, Investigation. Qipeng Zhao: Visu­
alization, Investigation. Yanchao Xu: Writing- Reviewing and Editing.
Liguo Shen: Writing- Reviewing and Editing. Hongjun Lin: Supervision.
Tai-Shung Chung:Writing- Reviewing and Editing, 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.
Data availability
No data was used for the research described in the article.
Acknowledgments
This work research was supported by Zhejiang Provincial Natural
Science Foundation of China under Grant No. LQ23E080008. Prof.
Chung likes to thank the Yushan Scholar Program supported by the
Ministry of Education, Taiwan.
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