1 s2.0 S1383586623017847 Main

Separation and Purification Technology 326 (2023) 124876
Contents lists available at ScienceDirect
Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur
Carbon-based quantum dots in fabrication and modification of membranes:

A review
Sevde Korkut a, b, Vahid Vatanpour a, b, c, *, Ismail Koyuncu a, b, *
a
National Research Center on Membrane Technologies, Istanbul Technical University, Maslak, 34469 Istanbul, Turkey
b
Department of Environmental Engineering, Istanbul Technical University, Maslak, 34469 Istanbul, Turkey
c
Department of Applied Chemistry, Faculty of Chemistry, Kharazmi University, Tehran 15719-14911, Iran
A R T I C L E I N F O A B S T R A C T
Keywords: A scientific breakthrough in membrane technologies using nanomaterials drives the development of new
Quantum dots nanocomposite structures to improve processes. Carbon-based quantum dots (CQDs) have risen to prominence in
Graphene quantum dots membrane applications due to their superior characteristics among carbon nanomaterials since 2013. In this
Membranes
review, we have summarized and discussed all pressure-, concentration-, temperature- and electrical potential-
Separations
Environment protection
driven membrane applications of carbon-based QDs. Firstly, the synthesis methods of CQDs such as graphene
QDs, carbon nanodots, carbonized polymer dots, and carbon dots are briefly summarized. Then, state-of-the-art
studies from membrane applications using CQD in its manufacture or modification were summarized. The in
fluence of nanocomposite structures created by adding different elements or compounds to the CQD chain was
also considered. The results explanations are then reviewed, along with the difficult features of the uses of CQD-
containing membranes in the future.
1. Introduction At their basal planes and surfaces, they contain substantial quantities of
carboxyl, epoxy, and hydroxyl groups, and the O presence varies be
Carbon, the main compound of all life forms, ensured an outstanding tween 5 and 50% in weight largely depending on the synthesis method
technological uptrend with different structures [1]. Carbon-based [4]. The introduction of functional groups and passivation on their
quantum dots (CQDs) are newly described members of carbon nano surface, forming better dispersions in a solvent, polymer, or water have
forms such that fullerene, graphene, carbon nanotubes (CNTs), and been provided by the presence of these groups [5].
nanodiamonds [1]. The CQDs were discovered unexpectedly during the The CQDs have recently piqued the interest of researchers due to
purification of arc-synthesized single-walled CNTs by Xu et al. in 2004 their unique nanometer size [6–9]. Their photoluminescence (PL) and
[2]. The CQDs are zero-dimensional (no dimension is larger than 100 nm size-dependent optical properties were discovered first and have been
(0D)) quasi or quasi-spherical carbon nanoparticles of diameter between extensively researched [5,10–12] in various fields, such as therapy
2 and 20 nm composed of carbon (C), oxygen (O), and hydrogen (H) [3]. [13–15], chemical sensing [16,17], bioimaging [18–20], energy-related
Abbreviations: Alg, Alginate; AEM, Anion exchange membrane; AEMFCs, Anion exchange membrane fuel cells; CA, Citric acid; CDs, Carbon dots; CNDs, Carbon
nanodots; CNMs, Carbon-based nanomaterials; CNTs, Carbon nanotubes; CPDs, Carbonized polymer dots; CNF, Cellulose nanofiber; CP, Concentration polarization;
CQDs, Carbon-based; DBP, Disinfection by-products; EOL, End-of-life; FCTF-1, 2D fluorinated covalent triazine framework; FO, Forward osmosis; FRR, Flux recovery
ratio; g-C3N4, Graphitic carbon nitride; GO, Graphene oxide; GOQDs, Graphene oxide Quantum dots; GQDs, Graphene Quantum dots; HCDs, Hydrophobic carbon
dots; HR-TEM, High-resolution transmission electron microscopy; HTC, Hydrothermal carbonization; IP, Interfacial polymerization; IPA, Isophthalic acid; Im-PSU,
Imidized polysulfone; J, Flux; LMH, L/m2⋅h; L-asp, L-aspartic acid; LbL, Layer-by-layer; MB, Methylene blue; MF, Microfiltration; MOF, Metal-organic framework;
MPD, m-phenylene diamine; NCDs, Nitrogen doped CDs; NF, Nanofiltration; NP-CDs, Nitrogen/phosphorus-doped carbon dots; NGQD, Nitrogen-doped GQD; OGQD,
Oxygen-passivated GQD; P, Permeability; PA, Polyamide; PAN, Polyacrylonitrile; PDA, Polydopamine; PEI, Polyethyleneimine; PES, Polyethersulfone; PL, Photo
luminescence; PQDs, Polymer-like QDs; PEM, Proton exchange membrane; PEMFCs, Proton exchange membrane fuel cells; PSU, Polysulfone; PV, Pervaporation;
PVDF, Polyvinylidene fluoride; QDs, Quantum dots; QCDs, Quaternized carbon dots; R, Rejection/retention; rGO, Reduced GO; RO, Reverse osmosis; TA, Tannic acid;
TFC, Thin film composite; TFN, Thin film nanocomposite; TMC, Trimesoyl chloride; TPC, Terephthaloyl chloride; UF, Ultrafiltration; ZIF-8, Zeolitic imidazole
framework.
* Corresponding authors at: National Research Center on Membrane Technologies, Istanbul Technical University, Maslak, 34469 Istanbul, Turkey.
E-mail addresses: [email protected] (V. Vatanpour), [email protected] (I. Koyuncu).
https://doi.org/10.1016/j.seppur.2023.124876
Received 11 June 2023; Received in revised form 7 August 2023; Accepted 20 August 2023
Available online 21 August 2023
1383-5866/© 2023 Elsevier B.V. All rights reserved.
S. Korkut et al. Separation and Purification Technology 326 (2023) 124876
applications [21,22], photocatalysis [23,24], and electrocatalysis [25]. 2. Carbon-based quantum dots
Some informative reviews discussed the potential bio-applications
[26–29], the photocatalytic activity [30], energy and electronic de 2.1. Definition, properties, and classification
vices [31], and membrane applications [3] of CQDs. Because of their
remarkable mechanical, conductive, and anti-bacterial capabilities, Materials with all dimensions measured at the nanoscale. As a result,
carbon-based nanomaterials (CNMs) have been widely exploited in at materials with no dimensions greater than 100 nm are referred to as
tempts to construct innovative membranes for water treatment and zero-dimension (0D) materials. A “dot” is a nanometer-sized object or
desalination with enhanced qualities. In some circumstances, utilizing particle in nanoscience, whereas a “Quantum dot” (QD) is a semi-
CNMs resulted in innovative membranes with high flux, high rejection, conductor nanostructure in the quantum-confined regime [1,49]. The
low fouling, and enhanced electrical, thermal, and mechanical proper QDs are fluorescent, semiconducting nanocrystals that can be coated
ties [32]. with hydrophilic or hydrophobic groups, are easily synthesized, have
As presented in Fig. 1, the first paper about use of “quantum dots” in low-cost advantages, and are between 2 and 20 nm in size [50,51] The
the membrane application is reported in 2005. Regarding CQDs, the first first developed QDs were synthesized under harsh synthesis conditions
paper was published in 2013. The number of applications has increased and contained toxic heavy metals such as cadmium, mercury, and lead
exponentially since 2017. In addition, more attention was paid to the use [51,52]. However, the discovery made by Xu et al. in 2004 revealed a
of graphene quantum dots (GQDs) in the fabrication of membranes. new QD system that does not contain poison and can be synthesized very
There are also a few review studies on this subject. Zhao et al. while easily and cheaply [2]. The CQDs were discovered during the prepara
focusing solely on membrane separation and anti-fouling investigations tive electrophoresis step in the purification of single-wall CNTs. Then,
[3], Rani et al. emphasized the photocatalyst feature and mentioned Sun et al. obtained CQDs by laser ablation of graphite powder and
wastewater applications [33]. Kim et al. attracted attention to the anti- cement [53].
fouling properties of graphene oxide (GO) and CQDs, reviving mem Since their discovery, CQDs (Fig. 2) have attracted a lot of research
brane modification research on the topic [34]. There is also a study that and are sometimes being named GQDs, carbon nanodots (CNDs),
focuses on the optical properties of carbon dots (CDs) and covers a broad carbonized polymer dots (CPDs), and carbon dots (CDs, C-dot) [1]. To
range of CD-polymer nanocomposites [35,36], as well as a review study avoid confusion, we must first establish a generalized nomenclature.
that discusses carbon-based materials utilized in the development of CNDs are non-quantum-confined amorphous quasi-spherical fluorescent
non-polyamide desalination membranes [37]. Current review topics nanocarbons (Fig. 2C). The CPDs (Fig. 2E), which are nano-assemblies of
include biosensor and biomedical studies [38–42], molecular-imprinted π-conjugated polymers, are often generated using nano-precipitation,
polymer sensors [43], ion-battery electrode production [44], catalyst nano-emulsification, or self-assembly and have a few traits with CDs,
production for VOC treatment [45,46], membrane applications of CDs such as good optical properties, high photo-stability, and good
[47] and photostability of CQDs [48]. In this review, we have compiled biocompatibility (Fig. 2D). When fluorescent nanocarbons exhibit
and discussed all pressure-, concentration-, temperature- and electrical quantum confinement and crystalline structure, they are classified as
potential-driven membrane applications of CQDs (CDs, GQDs, graphene CQDs or GQDs based on their shape. CQDs are spherical or quasi-
oxide quantum dots (GOQDs), and their doped forms). spherical structures composed of sp2 and sp3 hybridized carbon,
whereas GQDs are composed of sp2 hybridized graphitic cores and
carbonyl surface moieties. GQDs have primarily been synthesized using
the top-down approach, whereas CQDs have been synthesized using the
Fig. 1. Number of publications on membrane applications containing QDs and carbon-based QDs. (Source: Scopus, 06.08.2023. ((TITLE-ABS-KEY (“carbon quantum
dots”) or (“quantum dots”) or (“carbon dots”) or (“graphene quantum dots”) AND TITLE-ABS-KEY (membrane separation).
2
Fig. 2. Structural insight of (A) GQD, (B) CQD, (C) CNDs, (D) polymer dots, and (E) graphitic carbon nitride dots [1].
bottom-up approach. GQDs have a more “molecule-like” character than metal-free QDs with similar optical characteristics specially g-C3N4 QDs
a colloidal structure (Fig. 2A). The band gap energy of pristine graphene [9,58].
is 0 eV or close to 0 eV, GQDs can have different sizes and the same band Compared to spherical, tubular, and plate fillers, CQDs have zero-
gap energy (i.e. 3.4 eV) [54]. CQDs and GQDs’ have a surface rich in dimension nanomaterials from the graphene family. Because QDs
oxygen-containing functional groups. CQD and GQDs optical charac contain many GO layers, they carry the most desirable properties of GO
teristics are highly influenced by functional groups such as hydroxyl, as well as their unique properties. In addition, unlike bulk GO nano
carboxyl, and epoxy and most importantly making them dispersible in sheets, it exhibits characteristic electronic and optical properties with
water easily [54]. the help of large side effects and quantum confinement. Thanks to these
Graphitic carbon nitride (g-C3N4) is a tri-s-triazine patterned poly structures and their high solubility it separates from other carbon-based
meric material composed of C, N, and a few H that exhibits excellent materials such as CNTs, fullerene, graphene, etc. [10]. In addition,
physicochemical and catalytic properties (Fig. 2E). Unlike g-C3N4, N- looking at long-term in vivo studies, it induced lower cytotoxicity than
doped CDs are obtained by the interaction of citric acid (CA) with urea, micrometer-sized GO nanoplates. The thickness of GO nanosheets
thiourea or another N-source [55]. g-C3N4 are used in a significant part ranges from nanometers to several micrometers. Therefore, it is very
of sensor studies because their photostability and quantum efficiency are difficult to wrap the polymer network in a thin-film layer with a thick
high, and the synthesis mechanism is simple, environmentally friendly ness in the range of 0.2–1 μm produced by interfacial polymerization
and biocompatible [56]. In addition, hexagonal boron nitride QDs, (IP) and to obtain a defect-free nanocomposite membrane. Moreover,
which were first synthesized in 2014, have started to be the focus of since GO deposition cannot be completely avoided, non-selective
new-generation research with their similar properties [57]. Moreover, boundary defects can easily occur between the GO sheets and the
unusual optical and electronic characteristics can be brought when the polymer. The QDs have both small dimensions and a surface rich in
size of bulk g-C3N4 is reduced down to 10 nm to attain QDs due to functional groups that will help them adapt to the polymer [59].
occurring strong quantum confinement and edge effects with such a Comparing 0D CQDs with 1D, 2D, and 3D carbon-based nano
small size. For example, the conduction and valence bands of g-C3N4 materials, such as carbon nanotubes, graphene, and nanodiamond,
QDs are shield in reverse directions with respect to bulk g-C3N4, respectively, reveals several advantages of CQDs. One way to concep
resulting in a broader band gap and an important difference in the tualize 1D carbon-based nanomaterial CNTs is a cylindrical layer of
photophysical characteristics. In addition, metal-based QDs have graphene topped with fullerene structures [60]. A single layer of carbon
resulted some environmental worries because of the usage of heavy atoms make up the 2D hexagonal lattice known as graphene. It is pro
metals as the essential elements, which restricts their extensive use. posed to be the fundamental component of all graphitic forms, such as
Therefore, significant consideration has been paid to progress new fullerene, CNTs, and graphite [61]. Carbon single-crystal nanodiamonds
3
(3D) have larger than 200 m2/g specific surface area and hydrophilic 2.2.1. Top-down methods
surface owing to the presence of many oxygenated functional groups. In Chemical ablation: In this method, highly oxidizing acids are used
contrast to the sp2 carbon present in nanotubes and fullerenes, they are to carbonize small organic molecules in controlled conditions to obtain
made of sp3 carbon [62]. Firstly, in terms of simple synthesis, compared carbonaceous materials that can be split into small layers [4,65]. In
to other carbon-based nanomaterials like graphene or carbon nanotubes, addition, it is a challenging process with steps such as the purification of
CQDs can be relatively simple and cost-effective to synthesize. Several nanomaterials, neutralization of excessively acidic medium, and treat
green synthesis methods have been developed, using sustainable and ment of the resulting wastewater. One of the disadvantages of this
environmentally friendly approaches [42]. The tunable size and surface method is that it is difficult to control the resulting dots production of
chemistry of CQDs enable the design of membranes with controllable the desired size. In 2013 Shen et al. used chemical ablation to synthesize
size-selective properties [36]. CQDs can be incorporated into a wide photoluminescent CDs with the reflux of polyethyleneimine (PEI) as a
range of membrane matrix materials, including polymers, ceramics, and carbon source and nitric acid at 120 ◦ C [66]. Contrary to those in the
composite materials. Their small size and ability to form stable disper literature, these dots exhibited a pH-sensitive structure as pH increased
sions make them compatible with diverse fabrication techniques, such as from 2 to 12. With this feature, it can act as a proton sensor in cell im
solution casting, phase inversion, and electrospinning. CQDs are aging studies. However, as another disadvantage of this method, the
generally considered biocompatible and can be functionalized for spe quantum efficiency was 2%, and the particle size was relatively large at
cific biological interactions. This makes them suitable for applications in 12 nm.
bioseparation, bioremediation, and drug delivery through membrane- Electrochemical carbonization: The electrochemical method,
based systems [38]. Some CQDs possess inherent photocatalytic prop which can be applied at room temperature and under normal pressure, is
erties, which can be harnessed to develop self-cleaning and self- used in the electrolysis of graphite anodes [64]. The composition of the
regenerating membranes [63]. These photocatalytic CQDs can degrade liquid electrolyte is variable and a mixture for the desired CQD structure
organic pollutants and foulants under light irradiation, maintaining the can be used. This mechanism gives flexibility to electrochemical process
membrane’s functionality over extended periods. 0D CQDs possess [65]. The electrochemistry method of synthesis of CQDs has been
abundant surface functional groups, including hydroxyl, amino, and heavily publicized because it is simple to modify the particle size and PL
carboxyl groups. These functional groups can be easily modified, performance of the produced CQDs [67–76]. In Ahirwar et al. study,
allowing for tailoring their properties to suit specific applications [64]. GQDs/GOQDs were synthesized by electrochemical exfoliation method
[77]. While the electrolyte aqueous solution consists of NaOH and CA,
2.2. Synthesis techniques graphite rods are used as electrodes. Different CQDs were synthesized by
different electrochemical oxidations by keeping the CA concentration
The methods for synthesizing CQDs are classified as “top-down” and constant and changing the alkali hydroxide concentration. GQDs and
“bottom-up” [36]. The top-down method simply refers to the way a GOQDs with particle sizes of 2–3 nm radiated from blue to green with
macromolecule is shrunk into a nanoparticle. Top-down approaches 365 nm UV irradiation. The advantages of this method include
include chemical ablation, electrochemical carbonization, and laser controllable size and nanostructure, and obtaining a high uniform
ablation (Fig. 3). The bottom-up synthesis approach, on the other hand, diameter monodisperse output of 3–8 nm. The scarcity of materials that
means bringing relatively small molecules together. Bottom-up methods you will use as a precursor in the synthesis limits this method [78].
are microwave irradiation and hydrothermal/ solvothermal treatment, Laser ablation: This synthesis method involves irradiating a carbon
especially in membrane applications (Fig. 3). Top-down synthesis pro target with a laser to break it down into CQDs or CDs [79,80]. The laser
cesses require harsh conditions such as acids used for chemical oxidation ablation method is green, quick, efficient, simple, and heavily adaptable,
and a high-temperature environment, but provide high-efficiency pro but it has a low production rate, a low quantum yield, and high equip
duction. Bottom-up synthesis methods, which are advantageous in terms ment cost [81]. At first, Sun et al. first heat treated the graphite powder
of particle size and structure control, are time-consuming and multi-step and cement mixture, then produced CQDs by laser ablation in the system
[65]. where the carbon material was in an argon gas flow carrying water
vapor (via a water bubbler) at a temperature of 900 ◦ C and a pressure of
Fig. 3. Synthesis precursors and methods of CQDs.
4
75 kPa [53]. After 12 h of refluxing in nitric acid and passivating CQDs temperature resistance, and anti-fouling [93,94]. Aside from the afore
with simple organic species such as PEG1500N (amine-terminated mentioned benefits of TFC membranes, certain substantial downsides
polyethylene glycol) and poly propionyl ethyleneimine-co ethyl have been noted, limiting their practical use. The major one is linked to
eneimine, CQDs obtained highly luminescence emission around 5 nm. fouling, which rises operational costs and reduces membrane lifespan
Although this method has many benefits, such as simple structure and while impacting water flow and salt rejection [95]. By halting microbial
the ability to prepare a broad range of nanostructures, for the manu growth, chlorination prevents biological pollution. In desalination or
facture of carbon targets, this process necessitates a substantial volume separation processes where TFC membranes are used, the polyamide
of carbon material. The diameter of the carbon nanoparticles produced (PA) layer is not resistant to chlorine, the PA chain stretches and
by the laser irradiation technique varied greatly; large ones were easily hydrogen bonds are broken. This situation begins to reduce the life of the
selected during centrifugation, resulting in low carbon nanoparticle membranes. After chlorination at high pH, water flow limitation across
yields and carbon material use efficiency [65]. the membrane was observed [96].
A porous metal–organic framework (MOF) with good adsorption
2.2.2. Bottom-up approaches ability has come to the fore in RO/nanofiltration (NF) membrane
modification in recent years [97–99]. Wang et al. modified the glucose-
2.2.2.1. Direct pyrolysis. Microwave irradiation: Microwave irradia synthesized CQDs with zeolitic imidazole frameworks (ZIF-8), a MOF
tion of organic macromolecules is a quick, green, and cost-effective way based on zinc nitrate hexahydrate [84]. They investigated disinfection
to make CQDs [56,57]. When compared to other approaches, heating by-products (DBPs) removal from chlorinated water by TFN membrane
the carbon precursors more conveniently and quickly simplifies the production by dispersing the obtained CDs@ZIF-8 nanomaterials in the
synthesis process, allowing CQDs to be obtained in a matter of minutes aqueous phase of the IP reaction. With this modification made to remove
and with a higher yield. Most researchers have created CQDs from py DBPs by size sieving mechanism, the IP reaction accelerated and the
rolysis of CA utilizing microwave-assisted treatments for membrane average pore size decreased on the surface with increased hydrophilic
applications due to the inexpensive cost of precursors, simple mecha ity. The membrane with a maximum salt rejection rate of 98.2% was
nism, high production and quantum yield, and controllable particle size incorporated with 0.15% nanomaterials and the permeability was re
distribution [3]. ported as 1.9 LMH/bar. The removal efficiencies of a total of 9 pollutants
Hydrothermal/solvothermal treatment: Hydrothermal carbon in trihalomethanes, haloacetonitriles and haloketone species were over
ization (HTC) also known as solvothermal carbonization, is a non- 95% and the sacrificing group of CDs against chlorine was one of the
expensive, green, and low-level toxicity method for producing novel effective mechanisms.
carbon-based compounds derived from a variety of raw materials [82]. A titanium dioxide/CDs (TiO2/CDs) hydrophilic nanocomposite
Usually, an organic precursor mixture is sealed and reacted at high photocatalyst with varying concentrations was inserted in the PA layer.
temperatures in a hydrothermal reactor. CQDs were synthesized using Because of its photocatalytic activity, TiO2/CDs nanocomposite
HTC from a variety of precursors including glucose, CA, chitosan, ba demonstrated a higher flux recovery ratio (FRR) (from 94.4 to 97.1%)
nana juice, and corn stalk [83–90]. An example of a simple, environ after being exposed to UV light during the washing process. The negative
mentally friendly and large-scale synthesis of CQDs from a cheap and charge hydrophilic functional groups improved the desalination per
abundant natural precursor is the hydrothermal synthesis from orange formance of 99.2% NaCl rejection and pure water flux of 59.6 LMH for
juice. The mechanism of formation of CQDs involves hydrothermal 0.01 wt% TiO2/CDs membrane [100]. At the same time, CDs were
carbonization of the main components of orange juice, such as sucrose, thought to be useful in improving chlorine-resistance mechanisms. CD
glucose, fructose, CA, and ascorbic acid [91]. Because of their highly encapsulation, on the contrary, is critical for limiting leaching and
photostable and nontoxic property, these CQDs with sizes ranging from preventing membrane performance loss. The removal efficiency of the
1.5 to 4.5 nm might be used in bioimaging. Liu et al. carbonized chitosan pristine membrane decreased from 97.5% to 78.5% based on the results
in a hydrothermal reactor at 180 ◦ C for 12 h and reported the synthesis before and after chlorination [94,101].
of amino-added fluorescent CQDs. Such CQDs are used for bioimaging Obtaining CDs from end-of-life (EOL) RO membranes can be
thanks to their high quantum efficiency [87]. considered a step in the circular economy [102]. EOL RO membrane
modules are frequently disposed of as plastic trash, primarily through
3. CQDs in membrane modification landfilling. The feasibility of recycling through pyrolysis and subsequent
conversion of the resulting char into CDs via an H2O2-assisted hydro
3.1. RO/FO thermal process at 600 ◦ C generated oil (28 wt%), non-condensable gas
(17 wt%), and char (22 wt%). While oil and gas can be used as fuel and
Membrane-based separation technology, particularly the reverse chemical feedstock due to their high hydrocarbon content, char has been
osmosis (RO) technique, has received considerable attention in recent discovered to be an excellent precursor for the synthesis of functional
decades for producing clean water from different water sources [92]. It CDs. The obtained N (4.8%) and S (1.8%) doped CDs had excellent water
necessitates a high operating pressure, which generally results in dispersibility, limited size distribution of 1.3–6.8 nm, exceptional sta
expensive energy and operational expenses, limiting the extensive use of bility, and a strong blue fluorescence with a quantum yield of 6.24%.
RO processes. As a result, next-generation RO membranes with highly Table 1 summerized the application of different CQDs in fabrication and
permeable and good solute rejection at lower operating pressures are of modification of RO/FO membranes.
tremendous interest for lowering energy consumption and operational A semipermeable membrane is placed between two different con
costs [92]. The most widely used membranes in the market today are centration solutions in the forward osmosis (FO) process: a concentrated
thin-film composite (TFC) RO membranes obtained by IP reaction be draw solution and a more dilute feed solution. FO can overcome various
tween an aqueous and organic phase. Coating on an ultrafiltration (UF) drawbacks of hydraulic pressure-driven membrane processes by
membrane occurs by the reaction between m-phenylene diamine (MPD) employing the osmotic pressure differential to drive water permeation
in the aqueous phase and trimesoyl chloride (TMC) in the organic phase across the membrane [112]. There is a tradeoff when selecting draw
[93]. Superior permeability capabilities, monovalent salt rejection, and solutes between small solute size to reduce internal concentration po
high stability in alkaline and acidic conditions distinguish TFC mem larization (CP) and large solute size to lower reverse draw solute flow.
branes. By using the emerged nanomaterials in the production of next Indeed, eliminating reverse draw solute flux is one of the primary ben
generation thin-film nanocomposite (TFN) membranes, it has gained efits of polymer and nanoparticle-based draw solutions [113]. The
outstanding properties such as high hydrophilicity, chemical and optimal FO membrane has a high-water flux and mechanical strength, as
well as the ability to remove draw/feed solutions. The support layer is a
5
Table 1
RO and FO membranes containing CQDs and derivatives.
Membrane Carbon-based Synthesis method/precursor Aim of study/Main findings Ref.
type QDs
RO CDs Hydrothermal/glucose – The quantum size of CDs was 6.8 nm. CDs were dispersed into an aqueous phase with MPD [103]
– Water flux was increased by 19% that obtained 87.1 LMH
– Depending on the deposition time of CDs on the PSU substrate, flux and rejection were enhanced.
RO N-GOQDs Hydrothermal/CA – High hydrophilic surface (56◦ ) compared with bare PA layer (87◦ ) [7]
– Pw = 0.62 ≫ 1.66 (62%) LMH/bar
– Ps = 0.7 ≫ 1.87 LMH/bar
RO Na-CQDs Hydrothermal/CA – High-pressure compression (23 bar) shortened the route of the water channels, reduced resistance, and [92]
increased the interior surface area.
– Jw = 57.65 LMH, Rs = 98.6%
RO GOQDs Commercial – PSU support under 2 bar nitrogen at dead-end filtration system for occurring IP reaction. [6]
– By 120 h long-term test, strong anti-fouling properties against BSA and humic acid
– Pw = 1.54 ≫ 2.34 (34%) LMH/bar
– Ps = 0.38 ≫ 0.45 LMH/bar
FO GQDs Hydrothermal/ eucalyptus – GQDs were synthesized from eucalyptus leaves using a basic and green one-pot hydrothermal method. [104]
leaves – Nanofiber PES support was produced by the solution blow spinning method that provides 100% porosity.
– FRR value of 93.78%.
– Improvement of 16% in water flux.
FO GOQD/Ag Commercial – Triple layer includes PES/CNT/PA layer contributed GOQD/Ag [105]
– As adhesion is reduced, a high sterilization ratio was achieved S. aureus of 97.3% and E. coli at 99.8%.
– Brought membrane both anti-fouling and anti-bacterial properties by long-term release of Ag+
– Jw = 65.8 LMH and reverse salt flux Js = 1.4 g/m2.h
FO GQDs Hydrothermal/CA – GQDs have an average size of 2.19 nm. [106]
– Covalent bonds that between GQDs and PEI improved the stability during the filtration and hydraulic
cleaning process
– Water flux of 12.9 LMH and reverse salt flux of 1.41 g/m2.h
FO N-doped Hydrothermal /Waste corn – Affecting the degree of cross-linking, PDA also changed the membrane thickness [90]
CQDs stalks – Formed amide bonds (− CO − NH − ) as sacrificial sites provided resistance to chlorine.
– Shortening of permeable paths and enhancing of hydrophilicity provided low Jreverse salt/ Jwater values
(0.10–0.25)
FO CQD Hydrothermal and reflux/ – CQDs were synthesized using tulsi leaves and mixed with glycerol as a draw solution [107]
Tulsi leaves – Water flux is greater than that of a commonly used draw agent (NaCl), but with less reverse salt diffusion
– Simple recovery of diluted draw solution by filtration
FO GQDs/MnO2 Hydrothermal/CA – GQDs/MnO2 nanocomposite was added to the casting solution [108]
– A solid hydrogen bonding between nanocomposite-cellulose improved FO performance.
– Membranes with 0.5 and 0.7% GQDs/MnO2 immersed in 0.2 M NaCl salt solution retained their original
structure for 96 days.
FO NH2-GOQDs Hydrothermal/CA – The reaction of amino groups on NH2-GOQDs with acid chloride and carboxyl groups increased the degree [109]
of cross-linking of the PA layer, resulting in a compact surface.
– Jw = 26.57 LMH, Js = 6 g/m2.h
FO IPA-C-Dots Hydrothermal/ isophthalic – Room-temperature phosphorescence CDs derived from IPA [110]
acid – Anti-biofouling property by generation singlet oxygen (1O2) under light irradiation via energy transfer
from excited triplet state to dissolved triplet oxygen.
FO CQD Hydrothermal/oil palm – Added to PSU layer for 24 h by phase inversion [97]
biomass – Presence of carboxyl group, the surface of CQD was negative
– Anti-fouling mechanism by electrostatic repulsion
FO CQD Hydrothermal/CA − 24 h fouling test with TFN membranes [111]
– The permeate flux decreases by 40% (TFC) and 20% (TFN)
thin and porous sheet with small tortuous to shorten the diffusion path. pyrrolidinone-MPD) were used, not water, to disperse the HCDs, as
The active layer, on the other hand, is designed to keep the reverse salt evidenced in Fig. 4b. The synthesized HCDs have uniform size in the
flux to a minimum [114]. range of 3.0–5.0 nm diameter as presented in high-resolution trans
An ultra-low loading of GQDs during IP processes of an out-layer mission electron microscopy (HR-TEM) (Fig. 4c). In membranes to
selective hollow fiber membrane was achieved to improve the water which HCDs doped produced by the non-solvent induced phase sepa
permeability without loss of membrane selectivity [115]. Molecular ration (Fig. 4e), the stratification in the support layer was finger-like. In
dynamics simulation was used at the water-hexane and water-PA in addition, the micro-convex structures formed in the support layer pro
terfaces to investigate the effect of GQDs on the IP and membrane per moted the diffusion of the PA layer into the support layer (Fig. 4d).
formance. GQDs reduced the reaction rate during the IP process by Internal CP with non-resistance water channel pathways in the presence
lowering the diffusivities of MPD and TMC, according to the simulation of HCDs also provided attenuation. 10 wt% HCDs modified TFC-FO
results. Furthermore, when present in high concentrations near the PA membrane showed high flux (15.47 LMH) and low reverse salt flux
layer, GQDs reduced water permeability due to presenting like barriers (2.9 g/m2⋅h) by 1 M NaCl draw solution, compared to the unfilled
to water molecules. At very high concentration incorporating, GQDs membrane. This enhanced FO performance is ascribed to the lower
agglomerated at the water-hexane interface, reducing membrane structural factors of HCDs-induced water canals and reduced internal
selectivity due to defects by non-selective voids at the PA layer-GQD CP.
interface. IPA-C-dots were synthesized for obtaining room-temperature phos
Hydrophobic carbon dots (HCDs) were added to the polyacrylonitrile phorescence CDs derived from isophthalic acid (IPA) as a carbon pre
(PAN) support layer to strengthen the TFC-FO membrane [116]. At cursor [110]. TFN FO membranes containing conjugation of IPA-C-dots
ambient temperature, acetaldehyde aqueous solution and NaOH were with polylysine indicating a significant anti-biofouling property during
mixed to make HCDs (Fig. 4a) [116]. Unlike conventional CQDs, due to the static and dynamic bio-fouling resistant tests [117]. The reason for
their hydrophobic nature, organic solvents (e.g., ethanol, 1-methyl-2- this observation was that coupled IPA-C-dots can generate singlet
6
oxygen (1O2) under light irradiation via energy transfer from an excited PEI have more hydrophilic substances, which facilitates water flux. Also,
triplet state to dissolved triplet oxygen, which can be used as a photo the modified membrane grants lower loss in water flux during the anti-
dynamic anti-bacterial chemotherapy reagent. In addition, the anti- fouling test using 100 mg L− 1 BSA solution. CQDs reduced the film
fouling properties of CQDs were investigated both when added to the thickness, roughness and water contact angle of the membranes.
polymer matrix by phase inversion [97] and added to the active layer in In only one of the RO studies, the release of CQDs was noted and
the TFC FO membrane by IP [111]. Mahat et al. (2020) immersed the tested for it [105]. In the future, studies on the effects of CQD release
PSU support membrane layer directly in the CQD solution for 24 h [97]. from the surface on membrane performance need to be expanded. CQDs
Because of the carboxyl group, a CQD surface is negatively charged, incorporating FO membranes provided high water flux due to their loose
resulting in electrostatic repulsion with bacterial surfaces, which are structure but failed to keep the reverse salt flux at a low level. The
also negatively charged due to peptidoglycans in their cell wall. In development of draw solutions that can cause high osmotic pressure to
Seyedpour et al. study throughout 24 h fouling test, the permeate flux improve the FO process is an important research topic. Extraction so
decreases of 40% and 20% were observed for the TFC and TFN mem lutions that require little energy to reconcentrate, are low in ecotoxicity
branes, respectively [111]. or harmless and do not interact with the polymeric membrane used are
In Deng et al. study (2021), novel carbo polyether ketone-based FO ideal. In future, the development of drawing solutions that can cause
membranes were fabricated via layer-by-layer (LbL) self-assembly high osmotic pressure to improve the FO process is an important
method by exploiting CQDs as the negative layer and PEI as the posi research topic. Research to develop withdrawal solutions that do not
tive one (Fig. 5) [118]. The modified membrane portrayed superior require energy to reconcentrate, that are low in ecotoxicity or harmless
performance with a water flux of 30.8 LMH and a reverse salt flux of 8.9 and that do not interact with the polymeric membrane used are
g/m2.h. The fact that PEI is a positively charged polyelectrolyte caused it important.
to act as a wall against cationic Mg2+ ions and to stop the passage of In RO membranes, when the CQDs were added to IP phase even
Mg2+ ions with large molecular diameters. According to the data from lower than remaining substrate they worked well. The most important
the contact angle analysis, the membranes with the external surface of challenges in RO are chlorine resistance and increasing flux. Quantum
Fig. 4. (a) The synthesis procedure of hydrophobic carbon dots by acetaldehyde precursor. (b) HCDs solubility in different solvents. (c) HR-TEM images of HCDs. (d)
the schematic of channel regulation in the PAN support by addition of HCDs. (e) the schematic of fabrication of HCDs-decorated PAN membrane [116].
7
dots are materials that help overcome these two challenges. The func from CA and urea by the hydrothermal method and used for fabricating
tional group-rich surface of the quantum dots acts as a victim group CDs-PVDF membranes by mixed solvent phase separation method. The
against chlorine attack. In terms of increasing the flux, it shows a good surface of this membrane was hydrophobic avoids moisture buildup and
distribution in the IP reaction with dimensions less than 10 nm. Ag is still a dense layer that provided both ventilation and efficient filtration of
an indispensable element for anti-fouling, while Na+ doping increases particulate matters greater than 100 nm. Because, according to the SEM
the flux. High loading of nanoparticles caused agglomeration in the result, the pore diameters are less than 100 nm and are sufficient to
membrane structure. The presence of amine groups has the advantage of block the viral particles (Fig. 7a). CDs are in the structure as a photo
increasing the degree of crosslinking. Only one study has tested the thermal agent and the mask achieves self-sterilization by absorbing the
release of CQDs. This topic is open for further research following new visible light from the sun and at the same time it is heat dissipation with
methods. temperature rise as seen schematically in Fig. 7b. Future advancements
in the technique might lead to microbe, virus, and nanoparticle filtering
3.2. NF/UF/MF systems [133].
CDs-incorporated NF membranes using the phase inversion tech
The membrane surface is more hydrophilic not only enhances the nique achieved dye removal efficiency greater than 97.2% and Na2SO4
flux but also contributes to two aspects as an anti-fouling mechanism. removal rate of 80% [134]. Water contact angle values of 61.2◦ and
One of them is to prevent the directly binding of foulants to the surface 45.1◦ for the pristine and 1.0 wt% PES/CDs membranes, respectively,
by forming a hydration layer on the modified membrane surface. The demonstrated improved hydrophilicity of the CDs modified membranes.
other is to break the affinity of the contaminants to the surface and While the total fouling was 54.7% in the PES membrane, it decreased to
ensure that they are removed from the surface only by hydraulic 35.6% in the CDs added one. Findings established CDs as a suitable
washing [119,120]. membrane modification for desalination and wastewater treatment
In Wu et al. study, CA as a carbon source and L-aspartic acid (L-asp) goals [134].
as a nitrogen source were utilized to create L-asp-modified GQDs Koulivand et al. produced a PES NF membrane with anti-bacterial
(AGQDs) for providing more hydrophilic and reactive surface (Fig. 6a) properties by doping the CDs with nitrogen (NCDs) [135]. It was
[121]. The L-asp, one of the amino acids, contains two carboxyl (–OH) determined that while the FRR was 73.1%, it produced inhibition for
groups and an amine (–NH2) group in its structure and therefore is gram-negative and gram-positive bacteria. Cell membrane destruction is
highly preferred as a functionalizing agent. Amino acids are classified as one of the primary mechanisms of CDs anti-bacterial effect. This trait is
zwitterionic substances and grafting zwitterionic amino acids improve frequently observed when the CDs sharp edges touch the cell wall,
membrane fouling resistance on the membrane surface. AGQDs were resulting in cytoplasm leakage and altering the microorganism’s genetic
embedded to the PA active layer via IP process (Fig. 6b). The optimized process after binding to DNA and RNA. As a secondary anti-fouling
membrane portrayed a prominent water permeance of 18.5 LMH/bar, mechanism, hydroxyl (–OH) radicals found in NCDs have been used as
60.9% higher than the bare TFC membrane (Fig. 6c). As presented in anti-biotics against both S.aureus (gram-positive) and E. coli (gram-
Fig. 6d, the different salt retentions followed the order of Na2SO4 > negative).
MgSO4 > MgCl2 > NaCl (2000 ppm), which is consistent with the UiO-66-NH2 is a type of MOF containing amino and carboxyl groups
negatively charged NF membrane. on its surface. CQDs, on the other hand, have a structure rich in oxygen-
With the global pandemic of COVID-19, the manufacturing of high- containing functional groups. UiO-66-NH2@CQDs nanocomposite is an
sensitivity hygiene facemasks became crucial. Singh et al. reported in innovative material to improve hydrophilicity and fouling resistance
their study that it produced a face mask containing CDs-polyvinylidene [136]. The contact angle of PES UF membranes produced with the
fluoride (PVDF) composite film (Fig. 7a) [133]. CDs were synthesized addition of UiO-66-NH2@CQDs decreased from 85◦ to 59.8◦ compared
Fig. 5. (a) The synthesis procedure of negative charge CQDs by milk precursor. (b) HR-TEM images of the synthesized CQDs. (c) The fabrication steps of the layer-by-
layer (LbL) FO membrane by repeating coating of PEI and the CQDs on a PEK porous support [118].
8
to the bare membrane. While BSA removal was successful at the rate of canals (Fig. 8c). Second, the inclusion of QCDs improved ion exchange
95% and FRR was 77.6%, after 120 min of filtration the flux declined capacity and water uptake of the nanocomposite AEMs as illustrated in
and accumulation occurred in the membrane pores due to BSA mole Fig. 8d [86].
cules. Table 2 summerized the application of different CQDs in fabri In 2020, nanocomposite AEMs based on chloromethylated PSU were
cation and modification of NF/UF/MF membranes. created for the diffusion dialysis process in the acid recovery from
The presence of hydrophilic functional groups promoted the synthetic waste prepared by high concentration of acids and salts
dispersion of CQDs in aqueous solution and naturally increased the flux. [144,145]. The composites were made using varying weight percentages
It has been observed that the membrane performance is improved both (0.1, 0.5, and 1.0) of GQDs produced by chemical oxidation of MWCNTs
when used in IP and when added to the polymer matrix. It has provided a followed by quaternization by trimethylamine. Nanocomposite mem
new field of study by using CQDs in surgical masks with a PVDF branes outperform bare membranes in terms of water uptake, ion ex
membrane. change capacity, and mechanical stability. In the presence of metal ions,
modified membranes recovered 35.5–47.5% of the acid.
3.3. Ion exchange membranes PEMs, like AEMs, are being researched to provide strong methanol
resistance and high proton conductivity. At ideal water concentrations,
Electrochemical systems are drawn to CQDs with rapid electron perfluorosulfonic acid polymer, Nafion, is a typical PEM material which
transport and a wide surface area. Moreover, the abundance of is proven having stable performance and high level ionic (proton) con
heteroatom-containing functional groups (oxygen, nitrogen, sulfur, ductivity. The CA was used as the carbon source as it is suitable for low
phosphorus, boron, and so on) on 0D carbon nanomaterials provides a temperature (200 ◦ C) pyrolysis which does not degrade the functional
plethora of active regions and points for improved electrochemical ization reagent Nafion (Fig. 8e). Jia et al. modified the Nafion membrane
treatment performance. As a consequence, they may be capable to using synthesized Nafion decorated CDs for the same purposes and also
replace the current noble metal-based catalysts used in hydrogen evo to increase water uptake [142]. 0.5% Nafion decorated CDs doped
lution, oxygen reduction, and oxygen evolution processes [137]. Nafion hybrid PEM offers a five-fold increase in proton conductivity and
Fuel cells are predicted to revolutionize in future energy security. a 50% decrease in methanol permeability as compared to reformed
Fuel cell systems contain different elements such as anion exchange Nafion. Multi-functionalized Nafion decorated CDs having moderate
membrane fuel cells (AEMFCs), proton exchange membrane fuel cells level hydrophilicity alter the aggregation structure of the composite
(PEMFCs), direct alcohol fuel cells, phosphoric acid fuel cells, molten membranes Nafion matrix and successfully improve high temperature
carbonate fuel cells, and solid oxide fuel cells (ceramic ion-conducting water retention. During the fabrication process, multi-functionalized
electrolyte) [138]. The proton exchange membrane (PEM) is a crucial Nafion decorated CDs interact moderately with the Nafion matrix and
element of direct methanol fuel cells that transports protons and while influence its aggregation structure via hydrophilic and H-bonding
obstructing fuel in PEMFCs [139]. The PEM is a semi-permeable mem interactions.
brane that reserves the reactant gases and transfers protons. Commer The inclusion of CQDs shrinks the intrinsic pore diameters of the
cially readily accessible Nafion®3,4 membranes with a Nafion membrane while increasing the membrane’s ion conductivity
polytetrafluoroethylene skeleton and pendant short perfluoroether and mechanical strength. The CQDs-doped hybrid membranes should be
branches terminated with sulfonic acid groups have the obvious disad beneficial in the design and fabrication of innovative energy devices
vantages of massive cost, dehydration, and consequent decrease of such as fuel cells, metal-air cells, and flow batteries. The entire cost of
conductivity at higher temperatures as the state-of-the-art of PEMs fuel cell implementation remains high, and competition from other
[140,141]. On the contrary, they have elicited substantial inquiry from renewable energy devices is fierce. It is vital to develop precious metal-
the standpoint of the concept of chemical structure-morphology- free carbon-based catalyst materials to compensate for this loss. CQDs
property relationship, which sheds light on the exploration of their al and GQDs can be converted into low-cost hybrid materials. The fact that
ternatives. It is critical to develop a high-performance PEM having material synthesis is simpler and less harmful to the environment, as
strong proton conductivity, high mechanical strength and low perme well as the fact that the method is applicable at room temperature, are
ability to fuel and oxidant [140,142]. Anion exchange membrane also areas for improvement.
(AEM), a fundamental element of AEMFCs, is important for in fuel cell
blocking and anion transport. As a result, the efficiency of energy con 3.4. Photocatalytic membranes
version in AEMFCs is directly related to the performance of anion ex
change membranes (AEMs) [143]. Photocatalysis is a highly effective and environmentally acceptable
High conductivity, long term chemical stability, and low cost are the method of degrading organic macromolecule pollutants, especially
most targeted parameters in AEMs investigations. In Yuan et al. study, using sunlight as an energy source [146,147]. In photocatalytic tech
innovative nanocomposite AEMs were created by incorporating qua nologies, there is a wide range of information from material and energy
ternized carbon dots (QCDs) into an imidized polysulfone matrix (Im- source selection to the process to be applied, especially for removal of
PSU) [86]. QCDs were synthesized from CA and ethylenediamine fouling. Membrane fouling phenomenon caused by organic and inor
(Fig. 8a) with the aim of enhancing the ion transport channels. By ganic pollutants is a serious problem that negatively affects performance
including QCDs into the Im-PSU matrix, the OH– conductivity of the in all membrane processes [148]. Over time, foulants accumulate on the
nanocomposite AEMs was enhanced, as shown in Fig. 8b. The OH– membrane surface and inside the membrane pores causes gelation fol
conductivity of the nanocomposite AEMs at 25 ◦ C improved as the QCD lowed by concentration polarization and raises the osmotic pressure. CP
concentration increased, exceeding that of the bare Im-PSU membrane. will result in catastrophic membrane decline, which has become a
The ImPSU-1.0%-QCDs had roughly three times the OH– conductivity of bottleneck in osmotic pressure membrane-based applications
the bare Im-PSU membrane at 80 ◦ C, and this value increased from 86.9 [149,150].
mS/cm for Im-PSU membrane to 109.3 mS/cm for Im-PSU-1.0% QCDs. The primary goal of photocatalytic membrane fabrication research
This is primarily due to two factors: First, the surface of the QCDs had a was to create a functional surface or interlayer with (1) water transport
high concentration of conductive ionic groups such as quaternary paths for CP mitigation and (2) self-cleaning mechanism via photo
ammonium groups, therefore providing higher anionic conductivity in catalytic destruction of segregated organic pollutants [151,152].
the nanocomposite AEMs. The QCDs due to the great specific surface In Shao et al. study, CQDs-intercalated NF membrane was built out of
area can carry high quaternary ammonium groups to the nanocomposite a non-expensive polyethersulfone (PES) UF substrate and a PA layer
membranes, hence creating more hydrophilic ion clusters, and very coated by IP technique (Fig. 9a) [151]. The surface SEM of the resulted
concentrated ion clusters can produce long-range ordered ion transport membrane is presented in Fig. 9b. The highly selective PA layer can keep
9
Fig. 6. (a) Scheme of synthesis mechanism of AGQDs; (b) the fabrication process of modified TFN NF membrane by the AGQDs; (c) water flux and (d) salt rejection of
the prepared NF membranes as a function of AGQDs amount [121].
10
Fig. 7. (a) C-dot-PVDF nanoporous membrane for recyclable sunlight-sterilized anti-Covid-19 facemasks and SEM image of facemask as membrane, (b) schematic of
fabrication of the nanoporous C-dot-PVDF membrane [133].
CQDs from leaking. It also enhanced CQD photocatalytic reactivity by and structural properties, the possible mechanism to justify the influ
creating strong bonds between amide groups and CQDs, which is ence of membrane structures on CP mitigation, is illustrated in Fig. 9e.
assisted by a carboxyl activator, 2-chloro-1-methylpyridinium iodide. When anions encounter a rough surface, they show aggregation
Meanwhile, the PES substrate has low photostability and can be behavior and CP increases.
damaged by light irradiation [153]. Polydopamine (PDA) demonstrated By incorporating CQD/TiO2 nanoparticles, an IP polyamide TFN NF
remarkable free-radical scavenging abilities [154]. Furthermore, an membrane was fabricated having self-cleaning capability [155]. The
alkaline environment is conducive to polydopamine self- support layer was first coated with PDA to make it more stable of the
polymerization. As a result, a successive PDA-CQDs coating technique TFN NF membrane. The incorporation of CQD/TiO2 increased mem
was devised to both protect the substrate layer from physical/chemical brane hydrophilicity and provided the TFN NF membrane with high
damage and to enhance the membrane morphology via coordinated water flux (67.22 LMH), which was 1.8 times that of the pure NF
regulation. Through coordinated regulation, this is a possible way for membrane, as well as Na2SO4 salt rejection (96.7%). Concurrently, the
constructing high-performance membranes with both ultrafast transport produced TFN NF membranes demonstrated strong dye rejection to
channels and self-cleaning properties. The self-cleaning ability of the methyl blue (99.1%) and Congo red (99.8%). Furthermore, the mem
PDA/CQDs/TFC membrane was assessed by filtrating the 50 ppm branes’ visible light-induced photocatalytic degradation activity
methylene blue (MB) solution. The dye filtered membranes were irra allowed them to efficiently break down methyl blue dye molecules
diated for 30 min to degrade of the adsorbed dyes on the surface of absorbed via hydrophobic interactions on the active layer. In striking
membrane. The light irradiation steps were repeated twice to examine contrast to the results of cyclic physical cleaning, the FRR were sustained
the membrane stability. As shown in Fig. 9c, the permeability of pristine at 97–98% during the cyclic fouling-irradiation process without loss
TFC reduces from 5.13 to 3.32 LMH/bar, with 35.3% reduction after methyl blue rejections, exhibiting consistent and efficient self-cleaning
exposing twice. The color was still remained on the pristine membrane capabilities. Though after 72 h of continuous membrane fouling, the
surface after irradiation (Fig. 9d), showing the limited anti-fouling water flux was only reduced by 6.7% following visible light irradiation,
property. However, after CQDs addition, the PDA/CQDs/TFC pre outperforming the performance IP of bare TFN NF membrane (which
sented significantly improved photocatalytic self-cleaning and water was reduced by 23.4%). The produced TFN NF membrane via IP is
transport characteristics (Fig. 9c,d), due to the efficient photocatalytic extremely appropriate for efficient dye wastewater treatment due to its
property induced by CQDs. The MB adsorption totally removed after hydrophilicity and visible light-driven self-cleaning ability.
first irradiation. In addition, the PDA coating shielded the PES support The most important disadvantage of photocatalytic treatment is the
from damage by light irradiation. Based on the changes in morphology inability to deliver light sources into the membrane module operating
11
Table 2
Summarization some of UF/NF/MF studies used different types of CQDs.
Membrane Carbon-based QDs Synthesis method/precursor Aim of study/Main findings Ref.
type
NF L-asp-modified GQDs Hydrothermal/CA and L-Asp – L-aspartic acid improved anti-fouling capacity by grafting PVDF [121]
– WCA of 58.7◦ and water permeance 18.5 LMH/bar
− 98.4% Na2SO4 rejection
– Anti-fouling test with BSA (negatively charged) and lysozyme (positively charged).
BSA removal was better than lysozyme
NF CDs Microwave irradiation/CA – Sub-5 nm CDs synthesized and dopped into PEI matrix via IP reaction on PAN [122]
support to produce organic solvent NF
– Depending on the carbonation degree of CDs, the uptake of polar and non-polar
solvents varied.
– Isopropanol flux increased by 54.3% to 42.6 LMH
NF CQDs Hydrothermal/glucose – PEI cross-linked CQD added to the top layer of NF produced for biogas slurry [123]
valorization
– Above 90% concentration rates of amino acids from biogas slurry like lysine,
leucine, glutamic acid
– Permeability enhanced 3–4 folds
NF CDs Hydrothermal/CA and Zwitterions – To form of nonselective voids in PA layer and dense network [124]
hyperbranched PEI – Permeate flux increased by 2.8-fold (60.5 LMH)
– RNa2SO4 = 98.1%
– FRR value of 93.2% for the modified membrane
NF GQDs with amino/sulfonic Microwave-assisted pyrolysis/CA – Increasing to more than 2-fold higher water permeability [125]
modification and TAEA, 1, 3-PS – According to molecular simulation, the internal voids increased by 2-fold
– Pwater = 9.82 LMH/bar, RNa2SO4 = 97.4%.
NF CQDs Direct pyrolysis/CA – Loose NF used for real pretreated hairwork dyeing effluent [126]
– Maximum obtained water permeability of 56.0 LMH/bar
– Whole selected dyes were almost rejected completely (≥99.8%)
– FRR markedly enhanced from 79.1% to 98.5%.
NF CQDs Direct pyrolysis/CA and M-tolidine- – Tight NF used for real pretreated hairwork dyeing effluent [126]
H (MTH) – FRR value of 86.2% for the operating 72 h
– Pretreatment using flocculation with less dosage and cheap UF module
– Pwater = 4.31 LMH/bar, Rsalt = ≥96.4%
NF GQDs Direct pyrolysis/CA – Ultrathin loose PA nanofilm between aqueous and organic phases [127]
− 30 days stability in terms of operation and chlorine resistance
– Cl-/SO2−
4 selectivity was measured filtration of NaCl and Na2SO4 salts mixture as
205.8
– Pwater = 32.1 LMH/bar, RNa2SO4 = 99.6%
NF Carboxylic CQD (CCQD), Direct pyrolysis/CA, BPEI, PSS – TFN-NCQD showed different surface morphology from the others due to its cationic [128]
Amino CQD functional groups.
(NCQD)Sulfonated CQD – While TFN-SCQD was the most successful membrane in terms of anti-fouling, TFN-
(SCQD) NCQD standed out in the removal of divalent cations.
. – TFN-SCQD of Jwater = 42.1 LMH, RNa2SO4 = 93.6%
UF Ag/CQDs Hydrothermal/ lemon juice − 169% improvement of pure water permeability [129]
– Dye rejection with improvements of 192%
UF CQDs Commercial – Direct current electric field membrane forming device was used. [130]
– Water permeability of 280.1 LMH/bar, ~55% higher than bare
– BSA flux recovery rate reached 95.3%
UF CD/SiO2 Hydrothermal/Rice husk and SiO2 – Because of improved membrane hydrophilicity and pore expansion, 1.0 wt% CD/ [131]
SiO2 loading increased pure water permeability by 111%.
MF CD@CNF composite Hydrothermal /glutathione (GT) and – CD was in-situ synthesized and attached to cellulose nanofiber (CNF) [132]
citric acid (CA) – CD@CNF exhibited lower swelling and structural stability
– Rdye = 95% after third cycle for only cationic dyes; Jw= ~32 LMH/bar
under high pressure. This disadvantage is a critical factor preventing significantly increased the filtering performance and the retention ratio
photocatalytic purification from reaching industrial scale. A visible- [157]. The investigations are often performed in batches; however, with
light-induced photocatalytic membrane was created by depositing PEI- a continuous system, the real total regeneration time can be achieved.
g-C3N4 on a PDA coated membrane for very effective H2O2 generation CQDs can be said to aid in the development of active photocatalytic
(Fig. 10) [156]. The Fenton-like reaction was started when H2O2 came sites. This circumstance had a positive impact on dye removal efficiency.
into contact with a separation membrane with a FeOOH catalytic layer, The use of PDA extends membrane life in photocatalytic applications.
which was created using a co-deposition approach and then mineralized. Using biomass as a carbon source ensures a greener production process.
The organic molecules in the solution were oxidized by Fenton-like
catalytic reactions that created OH– radicals in the presence of photo 3.5. Pervaporation
generated H2O2, resulting in powerful surface cleansing, as seen in
Fig. 10. Pervaporation (PV) is a liquid/liquid separation process in which
Not only does GQDs have a greater capability for homogeneous mass transfer takes place according to the solution-diffusion model for
dispersion among photocatalyst materials, but it also serves as strong azeotropic or close boiling point mixtures [158]. Water molecules on the
acceptor like photocatalysts. In Safa et al. study, GQDs and UiO-66-NH2 feed side are adsorbed and dissolved into the PV membrane when they
suspension were prepared and deposited on the non-woven poly contact with the selective layer, and the absorbed water molecules travel
propylene membrane [157]. GQDs were synthesized by electrochemical to the permeate side of the membrane via internal water channels within
method from graphitic plate electrode. The results demonstrated that the dense layer [159].
the addition of GQDs significantly affects the recovery of membranes by Lecaros et al. conducted a series of studies for the use of CQDs in the
photocatalysis mechanism. The deposition of MOF on the membrane development of PV membranes [158,160–162]. GQDs were employed to
12
Fig. 8. (a) Schematic of CDs and QCDs syntheses; (b) anion conductivities and (c) water absorption and IEC of different AEMs in different contents of QCDs; (d)
mechanism of ion transport in ImPSU-x-QCDs membranes [86]; (e) the schematic of Nafion decorated CDs (NCDs) synthesis [142].
13
Fig. 9. (a) Fabrication process of photocatalytic nanofiltration membrane with PDA and CQDs interlayer and PA TFC layer for self-cleaning membrane. (b) Surface
SEM image of CQDs/PA membrane. (c) Stability of membranes after irradiation by visible light for 30 min. (d) Comparison photographs of membranes before and
after visible light irradiation. (e) Mechanism of concentration polarization on the bare and PDA/CQDs/TFC modified membrane [151].
potentially cover structural defects on reduced GO (rGO) graphitic re dimensional GO are identical to those of zero dimensional oxygen-
gions [158]. The obtained homo-structure nanocomposite fillers (rGO & passivated GQDs (OGQDs), but the size is different [162]. The
GQD) were mixed with an alginate solution to form a dense composite pressure-assisted self-assembly approach was used to create homo-
membrane for PV. Membranes were developed to separate alcohol/ structured membranes using GO and OGQDs. Curved cavities in the
water mixtures as they have high performance in separating low mo pure GO membrane appeared to increase flow, but n-butanol molecules
lecular weight alcohols The permeability flux of 2323 g/m2.h and the blocked these gaps, resulting in a loss of flow. In order to reduce the gap
permeate water concentration ratio of 92.7% was the membrane that between the GO nanosheets, the membrane was loaded with OGQDs,
made the best separation. The flux of rGO membranes without GQDs thus making the top layer a tight structure as can be seen in Fig. 11a. In
was higher than those with GQDs. This indicates that defects in the rGO the tightened GO-OGQD microfiltration (MF) membrane, the removal of
molecular structure cause quick transfer of molecules. The findings of curved spaces by the OGQDs prevented alcohol molecules from pene
this study suggested that GQDs might be used to seal or cure defects on trating the membrane. Instead, it allowed more water molecules to
rGO, which might be useful for the PV of alcohol/water mixtures. penetrate and pass through the oxidized layers. As a result, the presence
The molecular backbone and surface functional groups of two- of OGQDs improve water selectivity. The produced GO-OGQDs
14
Fig. 10. Schematic of single photocatalytic self-cleaning membrane, single Fenton-catalytic self-cleaning membrane, and sectional photocatalysis-membrane
cleaning technique [156].
composite MF membranes were utilized in order to discover the linkings a natural oligomer having rich phenolic groups that are more reactive
or bonds between the two carbonous nanomaterials as well as their in with acyl chloride groups [165]. The addition of 50 ppm NGQD during
fluence on n-butanol pervaporative dehydration. Through π-π in IP improved PV performance, allowing a 90/10 wt% n-butanol/water
teractions and hydrogen bonding, a stable nanocomposite lamella was mixture to be separated at 25 ◦ C. Since the number of hydroxyl groups in
created. At 100 ppm OGQD, the GO lamellae thickness decreased to 0.72 the structure of TPC is low, the obtained TA-TPC membrane was less
± 0.09 μm (Fig. 11a), compared to 1.28 ± 0.04 μm in pristine GO hydrophilic. At 3-min contact time, the TA-TMC-NGQD membrane had a
(Fig. 11b). The variations in thickness were likewise related to the flux total flux of 1100 g/m2.h and a water concentration in permeate of 97.1
trend, with the GO-OGQD100 having the thinnest layer with the highest wt%. The optimum modified membrane has rougher and more hydro
overall flux while separating 90/10 wt% n-BuOH/water combination at philic surface and smaller pores than bare TFC membrane.
25 ◦ C. The total flow was 945 g/m2.h, with a permeate water content of In Xiong et al. study, sulfonated CQDs were used with GO laminates
99.99 wt%. by cross-linking [163]. The cross-linking effect provided stability to the
In a study by Lecaros et al., PV performances were compared by structure to protect the GO interlayer spacing against swelling. The
adding nitrogen-doped GQD (NGQD) and OGQD to the alginate (Alg) sulfonated CQDs filled the spaces around the ordered edges of the GO
matrix [160]. Isopropanol/water mixture was used for PV dehydration nanosheets, resulting in increased hydrophilicity. The fixed spacing of
process. While OGQDs form strong H-bonds, NGQDs form weaker H- GO lamina and the infrequent vacancies presence around the nanoplates
bonds with alginate matrix but NGQDs are not released from the poly edges in the presence of sulfonated CQDs is helpful to improvement of
mer matrix by electrostatic attraction. The most important structural selective permeation of water (Fig. 11e).
characteristic in PV membranes is the free volume spaces and positron When compared to conventional dehydration membranes, CQDs
annihilation lifetime spectroscopy is used to measure it. As a result of the incorporated membranes exhibit a greater increase in permeation flux,
dry state analysis, it was determined that the free volume spaces of both implying that the shorter and less tortuous paths through layers favor
Alg-NGQD and Alg-OGQD membranes were less than the bare Alg water transport in the nanocomposite membranes. The long-term and
membrane. This proved an interaction between GQDs and Alg. In large-scale implications of dealing with these membranes must be
contrast, larger free volume voids were measured in the doped mem investigated. Membranes must be outfitted with CQDs of various func
branes in the wet state, the largest in the Alg-OGQD membranes. The tional groups in order to suit the industry’s demand for various purifi
overall flux achieved 5580 g/m2.h with a 99.95% water concentration in cation or separation applications.
permeate in dehydrating isopropyl alcohol/water (70/30 wt%) at 70 ◦ C
using Alg-OGQD membrane (Fig. 11c and d). The high penetration flux
and separation factor achieved in the Alg-OGQD membrane are 3.6. Gas separation
explained by the advantage of larger free volume voids. Considering the
long-term durability, which is an important factor for real scale appli Membranes containing nanomaterials can greatly increase mem
cations, Alg-OGQD membrane proved to be adequate with a water brane performance in terms of permeability or selectivity. In general,
content of more than 99% at 70 ◦ C permeate after 720 h of testing. gas separation polymeric membranes with nanoparticles can achieve
Similarly, Wang et al. mixed the GQDs into the sodium alginate matrix excellent performance through physically doped (dispersion, polarity,
for ethanol dehydration [164]. As a result of the performance tests, the and hydrogen-bonds) and chemically bonded techniques [166,167].
total permeation flux was obtained as 2432 g/m2⋅h with an increase of In Shi et al. work, molecular-level mixed matrix membranes were
60% compared to the bare membrane. fabricated by introducing two types of CQDs into Pebax (polyether-b-
Lecaros et al. aimed to increase the hydrophilicity of the PV mem amide copolymer): polymer-like QDs (PQDs) and GOQD [168]. PQD,
brane and prevent the mass transfer of large molecules by using NGQDs like other fillers, has been proven to degrade a portion of the inherent
in the two separate IP reaction between tannic acid (TA) and two acyl crystalline structure of Pebax. GOQD, on the other hand, contains some
chlorides (terephthaloyl chloride (TPC), and TMC [161]. TA was a good functional groups and generates an unusual increase of Pebax’s micro
alternative for the formation of a thin active layer during IP due to being phase separation. Different microphase structures occur from the addi
tion of PQD and GOQD in membrane matrix as seen in AFM (Fig. 12a)
15
Fig. 11. Cross-sectional SEM images of (a) homo-

structured nanocomposite GO/oxygen-passivated
GQDs (OGQDs) and (b) GO membranes fabricated
by the pressure-assisted self-assembly technique
[162]; (c) total flux and water concentration in
permeate and (d) separation factor and pervapora
tion separation index (PSI) of Alg-NGQD vs. Alg-
OGQD membranes [160]; (e) Schematic diagram
of the water molecules transportation pathway in
the membranes fabricated by the functional sulfo
nated CQDs introduced into 2D GO interlayer
confinement space [163].
and SEM micrographs (Fig. 12b). After loading GOQD, the PA nano dopped via IP reaction for fabricating TFN gas separation membranes
phase becomes more apparent in comparison to the bare membrane. The [88]. Thin-film coating using NP-CDs that the average particle diameter
PQD-embedded membrane showed the opposite trend. This reveals two of 2.6 nm was applied the outer side of hollow fiber PSU support layer.
distinct behaviors promoted by the inclusion of GOQD and PQD, cor The contact angles of the modified membranes were considerably
responding to enhanced microphase separation and, correspondingly, reduced from 65◦ to 9◦ by adding NP-CDs (0–1.5 wt%) to the PA layer,
collapse of the inherent structure in the Pebax matrix. The polyether indicating that the TFN membranes became significantly hydrophilic.
domains separate and become more accessible and selective for CO2 Water vapor permeance increased from 1511 to 2448 GPU in NP-CDs
penetration. As a filler, GOQDs performed better than PQDs with the loaded membrane according to bare TFC one. And also, H2O/N2 selec
addition of a lower concentration (Fig. 12c). High amount of functional tivity arised to 854 from 73. In TFN membranes, NP-CD nanoparticles
groups of PQDs destroyed the crystalline structures of polyether and with numerous hydrophilic functional groups bond with water mole
polyamide domains of Pebax. GOQDs, on the other hand, contains less cules and act as active sites for water molecules, resulting in increased
functional groups and improved Pebax microphase separation. The water vapor permeance.
performance of gas separation for all MMMs transcends the upper bound In Jiang et al. study, 2D fluorinated covalent triazine framework
reported in 2008 (Fig. 12e). Mostly, the Pebax/GQD-0.05 membrane (FCTF-1) derived from tetrafluoro dinitrile were synthesized [169].
showed 668 Barrer CO2 permeability and CO2/N2 selectivity of 101. The Several of the C-F bonds were broken during the preparation procedure,
water acts a significant role in such an outstanding performance. leading to a loss of some fluorine atoms. By converting the geometry and
Fig. 12d shows the water content of these membranes. Obviously, dimensions of FCTF-1 using piranha solution (a strong oxidant mixture
Pebax–GQD membrane presented a greater water content than of sulfuric acid and hydrogen peroxide), they were transformed into 0D
Pebax–PQD membrane. The effect of water-driven plasticization and COF QDs with very small particle size and rich in polar groups (Fig. 12f).
swelling effect can increase the d-spacing of polymer chains and Polar groups such as amidine, –OH show high affinity for CO2 molecules,
enhance the CO2 permeability. thus considerably improve membrane gas pair selectivity. Reducing the
Nitrogen/phosphorus-doped carbon dots (NP-CDs) nanoparticles nanoparticle size facilitates its dispersion in the solvent and ensures that
were obtained by a one-pot green technique from chitosan and were it is fully mixed into the polymer matrix.
16
Fig. 12. (a) AFM and (b) SEM images of Pebax, Pebax-GOQD-0.05, and Pebax-PQD-1 membranes. (c) Gas separation performance of membranes with different QDs
contents (binary gas, 25 ◦ C, 1 bar). (d) Water content and (e) Robeson’s upper bound for CO2/N2 separation performances (binary gas, 25 ◦ C, 1 bar) of Pebax–PQD
and Pebax–GQD membranes [168]. (f) A possible method for QD-FCTF-1 creation in piranha solution [169].
17
CQDs that synthesized by hydrothermal method using CA and EDA References

precursors dripped on porous alumina support and then thermal treat
ment the obtained membranes at temperature lower than 400 ◦ C under [1] S. Mandal, P. Das, Are carbon dots worth the tremendous attention it is getting:
challenges and opportunities, Appl. Mater. Today. 26 (2022), 101331, https://
argon [170]. At room temperature, the best separation factors for CO2/ doi.org/10.1016/j.apmt.2021.101331.
N2 and CO2/CH4 are up to 81.5 and 94.3, respectively. The permeation [2] X. Xu, R. Ray, Y. Gu, H.J. Ploehn, L. Gearheart, K. Raker, W.A. Scrivens,
process was linked to CO2 adsorption and desorption, together with the Electrophoretic analysis and purification of fluorescent single-walled carbon
nanotube fragments, J. Am. Chem. Soc. 126 (2004) 12736–12737.
size sieving effect. The CQDs membrane is a novel and very efficient [3] D.L. Zhao, T.S. Chung, Applications of carbon quantum dots (CQDs) in membrane
method of CO2 capture. technologies: a review, Water Res. 147 (2018) 43–49, https://doi.org/10.1016/j.
The molecular sieving mechanism begins with the adsorption of gas watres.2018.09.040.
[4] Y. Wang, A. Hu, Carbon quantum dots: synthesis, properties and applications,
molecules, the molecules diffuse into the membrane and then desorb. J. Mater. Chem. C. 2 (2014) 6921–6939, https://doi.org/10.1039/c4tc00988f.
The effective mechanisms in CQD membranes were adsorption and [5] X.T. Tian, X.B. Yin, Carbon dots, unconventional preparation strategies, and
desorption, and they played an important role in binary gas mixtures. An applications beyond photoluminescence, Small. 15 (2019) 1–30, https://doi.org/
10.1002/smll.201901803.
important contribution of CQDs is the enrichment of edge polar func
[6] X. Song, Q. Zhou, T. Zhang, H. Xu, Z. Wang, Pressure-assisted preparation of
tional groups with high affinity for the CO2 molecule. graphene oxide quantum dot-incorporated reverse osmosis membranes:
antifouling and chlorine resistance potentials, J. Mater. Chem. A. 4 (2016)
16896–16905, https://doi.org/10.1039/c6ta06636d.
4. Conclusion and perspectives [7] M. Fathizadeh, H.N. Tien, K. Khivantsev, Z. Song, F. Zhou, Polyamide/nitrogen-
doped graphene oxide quantum dots (N-GOQD) thin film nanocomposite reverse
In this review, we summarize the latest developments in the field of osmosis membranes for high flux desalination, Desalination. 451 (2019)
125–132, https://doi.org/10.1016/j.desal.2017.07.014.
CQD-modified membranes by compiling all membrane applications. [8] C. Zhang, K. Wei, W. Zhang, Y. Bai, Y. Sun, J. Gu, Graphene oxide quantum dots
With the discovery of CQDs in 2004, it was realized that a new era had incorporated into a thin film nanocomposite membrane with high flux and
begun both in the field of materials and in membrane technologies. antifouling properties for low-pressure nanofiltration, ACS Appl. Mater.
Interfaces. 9 (2017) 11082–11094.
CQD-based membrane applications, which are still at the research and
[9] A.Y. Goren, Y.K. Recepoglu, V. Vatanpour, Y. Yoon, A. Khataee, Insights into
development level, stand out to be transformed into commercial prod engineered graphitic carbon nitride quantum dots for hazardous contaminants
ucts because they are cost-friendly and contain many positive features at degradation in wastewater, Environ. Res. 223 (2023), 115408, https://doi.org/
10.1016/j.envres.2023.115408.
the same time.
[10] P. Tian, L. Tang, K.S. Teng, S.P. Lau, Graphene quantum dots from chemistry to
In terms of synthesis methods, we hope in the future to develop more applications, Mater. Today Chem. 10 (2018) 221–258.
cost-friendly, simple and large-scale product methods. Heteroatom [11] S.N. Baker, G.A. Baker, Luminescent carbon nanodots: emergent nanolights,
loadings such as N, O, P, S, which play a critical role in CQDs modifi Angew. Chem. Int. Ed. 49 (2010) 6726–6744.
[12] X. Wang, L. Cao, S. Yang, F. Lu, M.J. Meziani, L. Tian, K.W. Sun, M.A. Bloodgood,
cation by providing different improvements, can be enriched for various Y. Sun, Bandgap-like strong fluorescence in functionalized carbon nanoparticles,
purposes. Despite recent advances, more fundamental research and in- Angew. Chem. Int. Ed. 49 (2010) 5310–5314.
depth studies on membrane formation, fouling prevention mechanism, [13] Y. Wang, U. Kadiyala, Z. Qu, P. Elvati, C. Altheim, N.A. Kotov, A. Violi, J.
S. VanEpps, Anti-biofilm activity of graphene quantum dots via self-assembly
chlorine resistance, biofilm growth and toxicity in liquid separation with bacterial amyloid proteins, ACS Nano. 13 (2019) 4278–4289.
membranes are required for better scientific progress and industrial [14] A. Łoczechin, K. Séron, A. Barras, E. Giovanelli, S. Belouzard, Y.-T. Chen,
application. N. Metzler-Nolte, R. Boukherroub, J. Dubuisson, S. Szunerits, Functional carbon
quantum dots as medical countermeasures to human coronavirus, ACS Appl.
As seen with ion exchange membranes, CQDs have the necessary Mater. Interfaces. 11 (2019) 42964–42974.
functional groups and appropriate particle sizes for integration into [15] N. Gong, X. Ma, X. Ye, Q. Zhou, X. Chen, X. Tan, S. Yao, S. Huo, T. Zhang, S. Chen,
membranes currently in use. However, in the future, studies such as Carbon-dot-supported atomically dispersed gold as a mitochondrial oxidative
stress amplifier for cancer treatment, Nat. Nanotechnol. 14 (2019) 379–387.
establishing covalent bonds between phases can be directed to create
[16] J.-Y. Huang, L. Zhao, W. Lei, W. Wen, Y.-J. Wang, T. Bao, H.-Y. Xiong, X.-
more stable structures. It has been demonstrated that it helps to reduce H. Zhang, S.-F. Wang, A high-sensitivity electrochemical aptasensor of
concentration polarization in photocatalytic membranes. carcinoembryonic antigen based on graphene quantum dots-ionic liquid-nafion
nanomatrix and DNAzyme-assisted signal amplification strategy, Biosens.
In order to increase the application areas, the behavior and in
Bioelectron. 99 (2018) 28–33.
teractions of carbon-based quantum dots in the polymer matrix, the [17] L. Li, D. Liu, H. Mao, T. You, Multifunctional solid-state
dispersion ability in the polymer matrix or during the IP, the release electrochemiluminescence sensing platform based on poly (ethylenimine) capped
from the membrane matrix should be studied in depth. Efforts should be N-doped carbon dots as novel co-reactant, Biosens. Bioelectron. 89 (2017)
489–495.
made to preserve the nanocomposite membrane structure and improve [18] L. Cao, X. Wang, M.J. Meziani, F. Lu, H. Wang, P.G. Luo, Y. Lin, B.A. Harruff, L.
the separation efficiency, especially in unfavorable and harsh condi M. Veca, D. Murray, Carbon dots for multiphoton bioimaging, J. Am. Chem. Soc.
tions. Water permeability, selectivity and anti-fouling structure come to 129 (2007) 11318–11319.
[19] X. Liu, H. Jiang, J. Ye, C. Zhao, S. Gao, C. Wu, C. Li, J. Li, X. Wang, Nitrogen-
the fore in pressure driven membranes. Membranes modified with CQDs doped carbon quantum dot stabilized magnetic iron oxide nanoprobe for
appeared to improve these parameters. In addition, cost studies and pilot fluorescence, magnetic resonance, and computed tomography triple-modal in
scale studies should be encouraged. vivo bioimaging, Adv. Funct. Mater. 26 (2016) 8694–8706.
[20] Z. Liu, W. Chen, Y. Li, Q. Xu, Integrin αvβ3-targeted C-dot nanocomposites as
multifunctional agents for cell targeting and photoacoustic imaging of superficial
malignant tumors, Anal. Chem. 88 (2016) 11955–11962.
Declaration of Competing Interest [21] X. Yun, J. Li, X. Chen, H. Chen, L. Xiao, K. Xiang, W. Chen, H. Liao, Y. Zhu, Porous
Fe2O3 modified by nitrogen-doped carbon quantum dots/reduced graphene
oxide composite aerogel as a high-capacity and high-rate anode material for
The authors declare that they have no known competing financial
alkaline aqueous batteries, ACS Appl. Mater. Interfaces. 11 (2019) 36970–36984.
interests or personal relationships that could have appeared to influence [22] A. Macina, T.V. de Medeiros, R. Naccache, A carbon dot-catalyzed
the work reported in this paper. transesterification reaction for the production of biodiesel, J. Mater. Chem. A. 7
(2019) 23794–23802.
[23] S. Nayak, S.R. Prasad, D. Mandal, P. Das, Carbon dot cross-linked
Data availability polyvinylpyrrolidone hybrid hydrogel for simultaneous dye adsorption,
photodegradation and bacterial elimination from waste water, J. Hazard. Mater.
The data that has been used is confidential. 392 (2020), 122287.
[24] Y.-Y. Li, Y. Si, B.-X. Zhou, T. Huang, W.-Q. Huang, W. Hu, A. Pan, X. Fan, G.-
F. Huang, Interfacial charge modulation: carbon quantum dot implanted carbon
Acknowledgments nitride double-deck nanoframes for robust visible-light photocatalytic
tetracycline degradation, Nanoscale. 12 (2020) 3135–3145.
[25] Y. Wang, X. Liu, X. Han, R. Godin, J. Chen, W. Zhou, C. Jiang, J.F. Thompson, K.
This work was supported by Research Fund of the Istanbul Technical B. Mustafa, S.A. Shevlin, Unique hole-accepting carbon-dots promoting selective
University (Grant number: 43962).
18
carbon dioxide reduction nearly 100% to methanol by pure water, Nat. Commun. sulfone) and functionalized quantum dot with improved fuel cell performance at
11 (2020) 1–9. high temperatures, Int. J. Energy Res. 45 (2021) 21274–21292, https://doi.org/
[26] A. Zarei, V. Ghaffarian, Preparation and characterization of biodegradable 10.1002/er.7178.
cellulose acetate-starch membrane, Polym. Plast. Technol. Eng. 52 (2013) [50] M.A. Reed, J.N. Randall, R.J. Aggarwal, R.J. Matyi, T.M. Moore, A.E. Wetsel,
387–392, https://doi.org/10.1080/03602559.2012.752831. Observation of discrete electronic states in a zero-dimensional semiconductor
[27] P. Devi, S. Saini, K.-H. Kim, The advanced role of carbon quantum dots in nanostructure, Phys. Rev. Lett. 60 (1988) 535.
nanomedical applications, Biosens. Bioelectron. 141 (2019), 111158. [51] A.P. Alivisatos, Semiconductor clusters, nanocrystals, and quantum dots, Science
[28] T.K. Henna, K. Pramod, Graphene quantum dots redefine nanobiomedicine, (80-) 271 (1996) 933–937.
Mater. Sci. Eng. C. 110 (2020), 110651. [52] D.J. Norris, M. Nirmal, C.B. Murray, A. Sacra, M.G. Bawendi, Size dependent
[29] M.J. Molaei, A review on nanostructured carbon quantum dots and their optical spectroscopy of II–VI semiconductor nanocrystallites (quantum dots),
applications in biotechnology, sensors, and chemiluminescence, Talanta. 196 Z. Phys. D Atoms, Mol. Clust. 26 (1993) 355–357.
(2019) 456–478. [53] Y.-P. Sun, B. Zhou, Y. Lin, W. Wang, K.A.S. Fernando, P. Pathak, M.J. Meziani, B.
[30] Z. Zeng, S. Chen, T.T.Y. Tan, F.-X. Xiao, Graphene quantum dots (GQDs) and its A. Harruff, X. Wang, H. Wang, P.G. Luo, H. Yang, M.E. Kose, B. Chen, L.M. Veca,
derivatives for multifarious photocatalysis and photoelectrocatalysis, Catal. S.-Y. Xie, Quantum-sized carbon dots for bright and colorful photoluminescence,
Today. 315 (2018) 171–183, https://doi.org/10.1016/j.cattod.2018.01.005. J. Am. Chem. Soc. 128 (2006) 7756–7757, https://doi.org/10.1021/ja062677d.
[31] X. Li, M. Rui, J. Song, Z. Shen, H. Zeng, Carbon and graphene quantum dots for [54] M. Jani, J.A. Arcos-Pareja, M. Ni, Engineered zero-dimensional fullerene/carbon
optoelectronic and energy devices: a review, Adv. Funct. Mater. 25 (2015) dots-polymer based nanocomposite membranes for wastewater treatment,
4929–4947. Molecules. 25 (2020) 1–28, https://doi.org/10.3390/molecules25214934.
[32] Y. Manawi, V. Kochkodan, M.A. Hussein, M.A. Khaleel, M. Khraisheh, N. Hilal, [55] A. Safikhani, V. Vatanpour, S. Habibzadeh, M.R. Saeb, Application of graphitic
Can carbon-based nanomaterials revolutionize membrane fabrication for water carbon nitrides in developing polymeric membranes: a review, Chem. Eng. Res.
treatment and desalination? Desalination. 391 (2016) 69–88, https://doi.org/ Des. 173 (2021) 234–252, https://doi.org/10.1016/j.cherd.2021.07.020.
10.1016/j.desal.2016.02.015. [56] E. Budak, S. Aykut, M.E. Paşaoğlu, C. Ünlü, Microwave assisted synthesis of boron
[33] U.A. Rani, L.Y. Ng, C.Y. Ng, E. Mahmoudi, A review of carbon quantum dots and and nitrogen rich graphitic quantum dots to enhance fluorescence of
their applications in wastewater treatment, Adv. Colloid Interface Sci. 278 photosynthetic pigments, Mater. Today Commun. 24 (2020), 100975.
(2020), 102124, https://doi.org/10.1016/j.cis.2020.102124. [57] E. Budak, C. Ünlü, Boron regulated dual emission in B, N doped graphene
[34] A. Kim, J. Hak Kim, R. Patel, Modification strategies of membranes with quantum dots, Opt. Mater. (Amst). 111 (2021), 110577, https://doi.org/
enhanced anti-biofouling properties for wastewater treatment: a review, 10.1016/j.optmat.2020.110577.
Bioresour. Technol. 345 (2022), 126501, https://doi.org/10.1016/J. [58] T. Wang, C. Nie, Z. Ao, S. Wang, T. An, Recent progress in g-C3N4 quantum dots:
BIORTECH.2021.126501. synthesis, properties and applications in photocatalytic degradation of organic
[35] M. Zulfajri, S. Sudewi, S. Ismulyati, A. Rasool, M. Adlim, G.G. Huang, Carbon dot/ pollutants, J. Mater. Chem. A. 8 (2020) 485–502, https://doi.org/10.1039/
polymer composites with various precursors and their sensing applications: a c9ta11368a.
review, Coatings. 11 (2021) 1100, https://doi.org/10.3390/coatings11091100. [59] K. Jiang, Y. Wang, Z. Li, H. Lin, Afterglow of carbon dots: mechanism, strategy
[36] R. Wang, K.Q. Lu, Z.R. Tang, Y.J. Xu, Recent progress in carbon quantum dots: and applications, Mater. Chem. Front. 4 (2020) 386–399, https://doi.org/
synthesis, properties and applications in photocatalysis, J. Mater. Chem. A. 5 10.1039/c9qm00578a.
(2017) 3717–3734, https://doi.org/10.1039/c6ta08660h. [60] R. Das, M.E. Ali, S.B.A. Hamid, S. Ramakrishna, Z.Z. Chowdhury, Carbon
[37] Y. Wang, Q. Li, G. Tang, N. Zhang, Recent progress on carbon based desalination nanotube membranes for water purification: a bright future in water desalination,
membranes and carbon nanomaterial incorporated non-polyamide desalination Desalination. 336 (2014) 97–109, https://doi.org/10.1016/J.
membranes, J. Environ. Chem. Eng. 9 (2021), 105762, https://doi.org/10.1016/ DESAL.2013.12.026.
j.jece.2021.105762. [61] W. Yi, A. Khalid, N. Arshad, M.S. Asghar, M.S. Irshad, X. Wang, Y. Yi, J. Si,
[38] M. Pourmadadi, E. Rahmani, M. Rajabzadeh-Khosroshahi, A. Samadi, X. Hou, H.R. Li, Recent progress and perspective of an evolving carbon family
R. Behzadmehr, A. Rahdar, L.F.R. Ferreira, Properties and application of carbon from 0D to 3D: synthesis, biomedical applications, and potential challenges, ACS
quantum dots (CQDs) in biosensors for disease detection: a comprehensive Appl. Bio Mater. (2023), https://doi.org/10.1021/acsabm.3c00076.
review, J. Drug Deliv. Sci. Technol. 80 (2023), 104156, https://doi.org/10.1016/ [62] V. Vatanpour, E. Salehi, N. Sahebjamee, M. Ashrafi, Novel chitosan/polyvinyl
J.JDDST.2023.104156. alcohol thin membrane adsorbents modified with detonation nanodiamonds:
[39] A. Kalluri, B. Dharmadhikari, D. Debnath, P. Patra, C.V. Kumar, Advances in preparation, characterization, and adsorption performance, Arab. J. Chem. 13
structural modifications and properties of graphene quantum dots for biomedical (2020) 1731–1740.
applications, ACS Omega. 8 (2023) 21358–21376, https://doi.org/10.1021/ [63] D.L. Zhao, H. Jin, Q. Zhao, Y. Xu, L. Shen, H. Lin, T.S. Chung, Smart integration of
acsomega.2c08183. MOFs and CQDs to fabricate defect-free and self-cleaning TFN membranes for dye
[40] S. Sengupta, S. Pal, A. Pal, S. Maity, K. Sarkar, M. Das, A review on synthesis, removal, J. Memb. Sci. 679 (2023), 121706, https://doi.org/10.1016/J.
toxicity profile and biomedical applications of graphene quantum dots (GQDs), MEMSCI.2023.121706.
Inorganica Chim. Acta. 557 (2023), 121677, https://doi.org/10.1016/j. [64] X. Wang, Y. Feng, P. Dong, J. Huang, A mini review on carbon quantum dots:
ica.2023.121677. preparation, properties, and electrocatalytic application, Front. Chem. 7 (2019)
[41] M.R. Mahajan, S.N. Nangare, P.O. Patil, Nanosize design of carbon dots, graphene 671, https://doi.org/10.3389/fchem.2019.00671.
quantum dots, and metal–organic frameworks based sensors for detection of [65] T.C. Wareing, P. Gentile, A.N. Phan, Biomass-Based Carbon Dots: Current (2021),
chlorpyrifos in food and water: a review, Microchem. J. 193 (2023), 109056, https://doi.org/10.1021/acsnano.1c03886.
https://doi.org/10.1016/j.microc.2023.109056. [66] L. Shen, L. Zhang, M. Chen, X. Chen, J. Wang, The production of pH-sensitive
[42] P. Kadyan, R. Malik, S. Bhatia, A. Al Harrasi, S. Mohan, M. Yadav, S. Dalal, photoluminescent carbon nanoparticles by the carbonization of polyethylenimine
S. Ramniwas, S. Kumar Kataria, T. Arasu, Comprehensive review on synthesis, and their use for bioimaging, Carbon N. Y. 55 (2013) 343–349.
applications, and challenges of graphene quantum dots (GQDs), J. Nanomater. [67] J. Zhou, C. Booker, R. Li, X. Zhou, T.-K. Sham, X. Sun, Z. Ding, An electrochemical
(2023), https://doi.org/10.1155/2023/2832964. avenue to blue luminescent nanocrystals from multiwalled carbon nanotubes
[43] H. Chi, G. Liu, Carbon nanomaterial-based molecularly imprinted polymer (MWCNTs), J. Am. Chem. Soc. 129 (2007) 744–745.
sensors for detection of hazardous substances in food: recent progress and future [68] D.B. Shinde, V.K. Pillai, Electrochemical preparation of luminescent graphene
trends, Food Chem. 420 (2023), 136100, https://doi.org/10.1016/j. quantum dots from multiwalled carbon nanotubes, Chem. Eur. J. 18 (2012)
foodchem.2023.136100. 12522–12528.
[44] M. Shaker, T. Shahalizade, A. Mumtaz, M. Hemmati Saznaghi, S. Javanmardi, M. [69] L. Bao, Z. Zhang, Z. Tian, L. Zhang, C. Liu, Y. Lin, B. Qi, D. Pang, Electrochemical
A. Gaho, W. Cao, W. Hu, Z. Jin, Q. Ge, A.A.S. Ghazvini, A review on the role of tuning of luminescent carbon nanodots: from preparation to luminescence
graphene quantum dots and carbon quantum dots in secondary-ion battery mechanism, Adv. Mater. 23 (2011) 5801–5806.
electrodes, FlatChem. 40 (2023), 100516, https://doi.org/10.1016/j. [70] L. Zheng, Y. Chi, Y. Dong, J. Lin, B. Wang, Electrochemiluminescence of water-
flatc.2023.100516. soluble carbon nanocrystals released electrochemically from graphite, J. Am.
[45] A. Ahmad, M. Ali, A.G. Al-Sehemi, A.A. Al-Ghamdi, J.W. Park, H. Algarni, Chem. Soc. 131 (2009) 4564–4565.
H. Anwer, Carbon-integrated semiconductor photocatalysts for removal of [71] Q.-L. Zhao, Z.-L. Zhang, B.-H. Huang, J. Peng, M. Zhang, D.-W. Pang, Facile
volatile organic compounds in indoor environments, Chem. Eng. J. 452 (2023), preparation of low cytotoxicity fluorescent carbon nanocrystals by
139436, https://doi.org/10.1016/J.CEJ.2022.139436. electrooxidation of graphite, Chem. Commun. (2008) 5116–5118.
[46] J. Wen, L. Zhou, Q. Tang, X. Xiao, S. Sun, Photocatalytic degradation of organic [72] H. Ming, Z. Ma, Y. Liu, K. Pan, H. Yu, F. Wang, Z. Kang, Large scale
pollutants by carbon quantum dots functionalized g-C3N4: a review, Ecotoxicol. electrochemical synthesis of high quality carbon nanodots and their
Environ. Saf. 262 (2023), 115133, https://doi.org/10.1016/j. photocatalytic property, Dalt. Trans. 41 (2012) 9526–9531.
ecoenv.2023.115133. [73] H. Li, X. He, Z. Kang, H. Huang, Y. Liu, J. Liu, S. Lian, C.H.A. Tsang, X. Yang,
[47] N.A. Tran, N.T. Hien, N.M. Hoang, H.L.T. Dang, D.Q. Huy, T. Van Quy, N. S. Lee, Water-soluble fluorescent carbon quantum dots and photocatalyst design,
T. Hanh, N.H. Vu, V.D. Dao, Carbon dots in environmental treatment and Angew. Chem. Int. Ed. 49 (2010) 4430–4434.
protection applications, Desalination. 548 (2023), 116285, https://doi.org/ [74] J. Deng, Q. Lu, N. Mi, H. Li, M. Liu, M. Xu, L. Tan, Q. Xie, Y. Zhang, S. Yao,
10.1016/j.desal.2022.116285. Electrochemical synthesis of carbon nanodots directly from alcohols, Chem. Eur.
[48] S. Dua, P. Kumar, B. Pani, A. Kaur, M. Khanna, G. Bhatt, Stability of carbon J. 20 (2014) 4993–4999.
quantum dots: a critical review, RSC Adv. 13 (2023) 13845–13861, https://doi. [75] S. Anwar, H. Ding, M. Xu, X. Hu, Z. Li, J. Wang, L. Liu, L. Jiang, D. Wang, C. Dong,
org/10.1039/d2ra07180k. Recent advances in synthesis, optical properties, and biomedical applications of
[49] K. Hooshyari, H. Rezania, V. Vatanpour, M. Rastgoo-Deylami, H.R. Rajabi, New carbon dots, ACS Appl. Bio Mater. 2 (2019) 2317–2338.
blend nanocomposite membranes based on PBI/sulfonated poly(ether keto imide
19
[76] Y. Hou, Q. Lu, J. Deng, H. Li, Y. Zhang, One-pot electrochemical synthesis of deposition methods on structure and performance, J. Memb. Sci. 632 (2021),
functionalized fluorescent carbon dots and their selective sensing for mercury ion, 119356, https://doi.org/10.1016/j.memsci.2021.119356.
Anal. Chim. Acta. 866 (2015) 69–74, https://doi.org/10.1016/j. [100] H. Zarrabi, M.E.M.E. Yekavalangi, V. Vatanpour, A. Shockravi, M. Safarpour,
aca.2015.01.039. Improvement in desalination performance of thin film nanocomposite
[77] S. Ahirwar, S. Mallick, D. Bahadur, Electrochemical method to prepare graphene nanofiltration membrane using amine-functionalized multiwalled carbon
quantum dots and graphene oxide quantum dots, ACS Omega. 2 (2017) nanotube, Desalination. 394 (2016) 83–90, https://doi.org/10.1016/j.
8343–8353. desal.2016.05.002.
[78] P. Zuo, X. Lu, Z. Sun, Y. Guo, H. He, A review on syntheses, properties, [101] V. Vatanpour, S.S. Madaeni, A.R. Khataee, E. Salehi, S. Zinadini, H.A. Monfared,
characterization and bioanalytical applications of fluorescent carbon dots, TiO2 embedded mixed matrix PES nanocomposite membranes: Influence of
Microchim. Acta. 183 (2016) 519–542, https://doi.org/10.1007/s00604-015- different sizes and types of nanoparticles on antifouling and performance,
1705-3. Desalination. 292 (2012) 19–29, https://doi.org/10.1016/j.desal.2012.02.006.
[79] H. Li, Y. Zhang, J. Ding, T. Wu, S. Cai, W. Zhang, R. Cai, C. Chen, R. Yang, [102] L. Liang, A. Veksha, M.Z. Bin Mohamed Amrad, S.A. Snyder, G. Lisak,, Upcycling
Synthesis of carbon quantum dots for application of alleviating amyloid-β of exhausted reverse osmosis membranes into value-added pyrolysis products and
mediated neurotoxicity, Colloid. Surf. B Biointerf. 212 (2022), 112373. carbon dots, J. Hazard. Mater. 419 (2021), 126472, https://doi.org/10.1016/j.
[80] H.-R. Chen, W.-M. Meng, R.-Y. Wang, F.-L. Chen, T. Li, D.-D. Wang, F. Wang, S.-E. jhazmat.2021.126472.
Zhu, C.-X. Wei, H.-D. Lu, Engineering highly graphitic carbon quantum dots by [103] Y. Li, S. Li, K. Zhang, Influence of hydrophilic carbon dots on polyamide thin film
catalytic dehydrogenation and carbonization of Ti3C2Tx-MXene wrapped nanocomposite reverse osmosis membranes, J. Memb. Sci. 537 (2017) 42–53,
polystyrene spheres, Carbon N. Y., 2022. https://doi.org/10.1016/j.memsci.2017.05.026.
[81] N. Shorgar, I. Bhati, P. Jhalora, Laser ablation synthesis of quantum dots, in: [104] H. Saleem, A. Saud, N. Munira, P.S. Goh, A.F. Ismail, H.R. Siddiqui, S.J. Zaidi,
Elsevier, 2023, pp. 53–75. Improved forward osmosis performance of thin film composite membranes with
[82] M.-M. Titirici, M. Antonietti, Chemistry and materials options of sustainable graphene quantum dots derived from eucalyptus tree leaves, Nanomaterials. 12
carbon materials made by hydrothermal carbonization, Chem. Soc. Rev. 39 (2022), https://doi.org/10.3390/nano12193519.
(2010) 103–116. [105] D. Wang, S. Li, F. Li, J. Li, N. Li, Z. Wang, Thin film nanocomposite membrane
[83] Z.-C. Yang, M. Wang, A.M. Yong, S.Y. Wong, X.-H. Zhang, H. Tan, A.Y. Chang, with triple-layer structure for enhanced water flux and antibacterial capacity, Sci.
X. Li, J. Wang, Intrinsically fluorescent carbon dots with tunable emission derived Total Environ. 770 (2021), 145370.
from hydrothermal treatment of glucose in the presence of monopotassium [106] S. Xu, F. Li, B. Su, M.Z. Hu, X. Gao, C. Gao, Novel graphene quantum dots (GQDs)-
phosphate, Chem. Commun. 47 (2011) 11615–11617. incorporated thin film composite (TFC) membranes for forward osmosis (FO)
[84] F. Wang, T. Zheng, R. Xiong, P. Wang, J. Ma, CDs@ZIF-8 modified thin film desalination, Desalination. 451 (2019) 219–230, https://doi.org/10.1016/j.
polyamide nanocomposite membrane for simultaneous enhancement of chlorine- desal.2018.04.004.
resistance and disinfection byproducts removal in drinking water, ACS Appl. [107] K. Doshi, A.A. Mungray, Bio-route synthesis of carbon quantum dots from tulsi
Mater. Interfaces. 11 (2019) 33033–33042, https://doi.org/10.1021/ leaves and its application as a draw solution in forward osmosis, J. Environ.
acsami.9b11006. Chem. Eng. 8 (2020), 104174, https://doi.org/10.1016/j.jece.2020.104174.
[85] S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin, K. Zhang, H. Sun, H. Wang, [108] H. Jain, A. Kumar, V.D. Rajput, T. Minkina, A.K. Verma, S. Wadhwa, R. Dhupper,
B. Yang, Highly photoluminescent carbon dots for multicolor patterning, sensors, M. Chandra Garg, H. Joshi, Fabrication and characterization of high-performance
and bioimaging, Angew. Chem. 125 (2013) 4045–4049. forward-osmosis membrane by introducing manganese oxide incited graphene
[86] Y. Yuan, B. Hu, C. Tong, Y. Bai, C. Lü, Novel quaternized carbon dots modified quantum dots, J. Environ. Manage. 305 (2022), 114335, https://doi.org/
polysulfone-based anion exchange membranes with improved performance, Int. 10.1016/j.jenvman.2021.114335.
J. Hydrogen Energy. 44 (2019) 22181–22193, https://doi.org/10.1016/j. [109] Z. Xu, P. Li, N. Li, W. Wang, C. Guo, M. Shan, X. Qian, Constructing dense and
ijhydene.2019.06.173. hydrophilic forward osmosis membrane by cross-linking reaction of graphene
[87] Y. Yang, J. Cui, M. Zheng, C. Hu, S. Tan, Y. Xiao, Q. Yang, Y. Liu, One-step quantum dots with monomers for enhanced selectivity and stability, J. Colloid
synthesis of amino-functionalized fluorescent carbon nanoparticles by Interface Sci. 589 (2021) 486–499.
hydrothermal carbonization of chitosan, Chem. Commun. 48 (2012) 380–382. [110] R. Knoblauch, C.D. Geddes, Carbon nanodots in photodynamic antimicrobial
[88] Y.M. Shirke, A.M. Abou-Elanwar, W.K. Choi, H. Lee, S.U. Hong, H.K. Lee, J. therapy: a review, Materials (Basel). 13 (2020), https://doi.org/10.3390/
D. Jeon, Influence of nitrogen/phosphorus-doped carbon dots on polyamide thin ma13184004.
film membranes for water vapor/N2 mixture gas separation, RSC Adv. 9 (2019) [111] S.F. Seyedpour, A. Rahimpour, A.A. Shamsabadi, M. Soroush, Improved
32121–32129, https://doi.org/10.1039/c9ra06300e. performance and antifouling properties of thin-film composite polyamide
[89] B. De, N. Karak, A green and facile approach for the synthesis of water soluble membranes modified with nano-sized bactericidal graphene quantum dots for
fluorescent carbon dots from banana juice, Rsc Adv. 3 (2013) 8286–8290. forward osmosis, Chem. Eng. Res. Des. 139 (2018) 321–334, https://doi.org/
[90] D. Wang, Y. Zhang, Z. Cai, S. You, Y. Sun, Y. Dai, R. Wang, S. Shao, J. Zou, Corn 10.1016/j.cherd.2018.09.041.
stalk-derived carbon quantum dots with abundant amino groups as a selective- [112] T.-S. Chung, S. Zhang, K.Y. Wang, J. Su, M.M. Ling, Forward osmosis processes:
layer modifier for enhancing chlorine resistance of membranes, ACS Appl. Mater. yesterday, today and tomorrow, Desalination. 287 (2012) 78–81.
Interfaces. 13 (2021) 22621–22634, https://doi.org/10.1021/acsami.1c04777. [113] T.Y. Cath, A.E. Childress, M. Elimelech, Forward osmosis: principles, applications,
[91] S. Sahu, B. Behera, T.K. Maiti, S. Mohapatra, Simple one-step synthesis of highly and recent developments, J. Memb. Sci. 281 (2006) 70–87.
luminescent carbon dots from orange juice: application as excellent bio-imaging [114] D.L. Shaffer, J.R. Werber, H. Jaramillo, S. Lin, M. Elimelech, Forward osmosis:
agents, Chem. Commun. 48 (2012) 8835–8837. where are we now? Desalination. 356 (2015) 271–284, https://doi.org/10.1016/
[92] W. Gai, D.L. Zhao, T.S. Chung, Thin film nanocomposite hollow fiber membranes J.DESAL.2014.10.031.
comprising Na+-functionalized carbon quantum dots for brackish water [115] N. Akther, Y. Kawabata, S. Lim, T. Yoshioka, S. Phuntsho, H. Matsuyama, H.
desalination, Water Res. 154 (2019) 54–61, https://doi.org/10.1016/j. K. Shon, Effect of graphene oxide quantum dots on the interfacial polymerization
watres.2019.01.043. of a thin-film nanocomposite forward osmosis membrane: an experimental and
[93] W. Gai, Y. Zhang, Q. Zhao, T.S. Chung, Highly permeable thin film composite molecular dynamics study, J. Memb. Sci. 630 (2021), 119309, https://doi.org/
hollow fiber membranes for brackish water desalination by incorporating amino 10.1016/j.memsci.2021.119309.
functionalized carbon quantum dots and hypochlorite treatment, J. Memb. Sci. [116] Z. Zhang, J. Hu, S. Liu, X. Hao, L. Li, G. Zou, H. Hou, X. Ji, Channel regulation of
620 (2021), 118952, https://doi.org/10.1016/j.memsci.2020.118952. TFC membrane with hydrophobic carbon dots in forward osmosis, Chinese Chem.
[94] V. Vatanpour, S. Paziresh, S. Ali, N. Mehrabani, S. Feizpoor, A. Habibi-yangjeh, Lett. 32 (2021) 2882–2886, https://doi.org/10.1016/j.cclet.2021.03.028.
I. Koyuncu, TiO2/CDs modified thin-film nanocomposite polyamide membrane [117] W. Miao, W.S. Zou, Q. Zhao, Y. Wang, X. Chen, S. Wu, Z. Liu, T. Xu, Coupling
for simultaneous enhancement of antifouling and chlorine-resistance room-temperature phosphorescence carbon dots onto active layer for highly
performance, Desalination. 525 (2022), 115506, https://doi.org/10.1016/j. efficient photodynamic antibacterial chemotherapy and enhanced membrane
desal.2021.115506. properties, J. Memb. Sci. 639 (2021), 119754, https://doi.org/10.1016/j.
[95] Y. Yao, X. Zhang, Chlorine resistant reverse osmosis membrane: a call for reform memsci.2021.119754.
of desalination treatment processes, Desalination. 501 (2021), 114907, https:// [118] Y.H. Deng, J.H. Chen, Q. Yang, Y.Z. Zhuo, Carbon quantum dots (CQDs) and
doi.org/10.1016/j.desal.2020.114907. polyethyleneimine (PEI) layer-by-layer (LBL) self-assembly PEK-C-based
[96] X. Zhang, H. Huang, X. Li, J. Wang, Y. Wei, H. Zhang, Bioinspired chlorine- membranes with high forward osmosis performance, Chem. Eng. Res. Des. 170
resistant tailoring for polyamide reverse osmosis membrane based on tandem (2021) 423–433, https://doi.org/10.1016/j.cherd.2021.04.026.
oxidation of natural α-lipoic acid on the surface, J. Memb. Sci. 618 (2021), [119] G. Zhao, R. Hu, J. Li, H. Zhu, Graphene oxide quantum dots embedded
118521, https://doi.org/10.1016/j.memsci.2020.118521. polysulfone membranes with enhanced hydrophilicity, permeability and
[97] N.A. Mahat, S.A. Shamsudin, N. Jullok, A.H. Ma’Radzi, Carbon quantum dots antifouling performance, Sci. China Mater. 62 (2019) 1177–1187, https://doi.
embedded polysulfone membranes for antibacterial performance in the process of org/10.1007/s40843-019-9417-5.
forward osmosis, Desalination. 493 (2020), 114618, https://doi.org/10.1016/j. [120] N.H. Zainal Abidin, S.N.A. Shafie, H. Suhaimi, N.S. Sambudi, N.A.H. Sapiaa Md
desal.2020.114618. Nordin,, Incorporation of carboxyl and amino functionalized carbon quantum
[98] M. Qun Seah, W. Jye Lau, P. Sean Goh, H.-H. Tseng, R. Abdul Wahab, A., Fauzi dots in thin film membrane for nanofiltration, Polym. Test. 100 (2021), 107270,
Ismail, polymers progress of interfacial polymerization techniques for polyamide https://doi.org/10.1016/j.polymertesting.2021.107270.
thin film (nano)composite membrane fabrication: a comprehensive review, [121] W.S.C. Wu, Q. Xie, Z. Hong, L. Shen, T. Yu, H. Guo, Y. Xiong, G. Zhang, Y. Lu,
Polymers (Basel) 12 (2020) 2817, https://doi.org/10.3390/polym12122817. Thin-film nanocomposite nanofiltration membrane with enhanced desalination
[99] X. Wu, L. Yang, F. Meng, W. Shao, X. Liu, M. Li, ZIF-8-incorporated thin-film and antifouling performance via incorporating L-aspartic acid functionalized
nanocomposite (TFN) nanofiltration membranes: importance of particle graphene quantum dots, Desalination. 498 (2021), 114811.
20
[122] Z. Yuan, X. Wu, Y. Jiang, Y. Li, J. Huang, L. Hao, J. Zhang, J. Wang, Carbon dots- [145] V. Yadav, S.K. Raj, N.H. Rathod, V. Kulshrestha, Polysulfone/graphene quantum
incorporated composite membrane towards enhanced organic solvent dots composite anion exchange membrane for acid recovery by diffusion dialysis,
nanofiltration performance, J. Memb. Sci. 549 (2018) 1–11, https://doi.org/ J. Memb. Sci. 611 (2020), 118331, https://doi.org/10.1016/J.
10.1016/j.memsci.2017.11.051. MEMSCI.2020.118331.
[123] W.J. Yang, D.D. Shao, Z. Zhou, Q.C. Xia, J. Chen, X.L. Cao, T. Zheng, S.P. Sun, [146] H. Zhang, Y. Wan, J. Luo, S.B. Darling, Drawing on membrane photocatalysis for
Carbon quantum dots (CQDs) nanofiltration membranes towards efficient biogas fouling mitigation, ACS Appl. Mater. Interfaces. 13 (2021) 14844–14865, https://
slurry valorization, Chem. Eng. J. 385 (2020), 123993, https://doi.org/10.1016/ doi.org/10.1021/acsami.1c01131.
j.cej.2019.123993. [147] N. Nasrollahi, L. Ghalamchi, V. Vatanpour, A. Khataee, Photocatalytic-membrane
[124] H. Zheng, Z. Mou, K. Zhou, Incorporation of core-shell-structured zwitterionic technology: a critical review for membrane fouling mitigation, J. Ind. Eng. Chem.
carbon dots in thin-film nanocomposite membranes for simultaneously improved 93 (2021) 101–116, https://doi.org/10.1016/j.jiec.2020.09.031.
perm-selectivity and antifouling properties, ACS Appl. Mater. Interfaces. 12 [148] R. Keyikoglu, O. Karatas, H. Rezania, M. Kobya, V. Vatanpour, A. Khataee,
(2020) 53215–53229, https://doi.org/10.1021/acsami.0c13386. A review on treatment of membrane concentrates generated from landfill leachate
[125] Y. Lin, Q. Shen, Y. Kawabata, J. Segawa, X. Cao, K. Guan, T. Istirokhatun, treatment processes, Sep. Purif. Technol. 259 (2021), 118182, https://doi.org/
T. Yoshioka, H. Matsuyama, Graphene quantum dots (GQDs)-assembled 10.1016/j.seppur.2020.118182.
membranes with intrinsic functionalized nanochannels for high-performance [149] J.R. McCutcheon, M. Elimelech, Influence of concentrative and dilutive internal
nanofiltration, Chem. Eng. J. (2020), 127602, https://doi.org/10.1016/j. concentration polarization on flux behavior in forward osmosis, J. Memb. Sci. 284
cej.2020.127602. (2006) 237–247, https://doi.org/10.1016/J.MEMSCI.2006.07.049.
[126] Y. Song, X. Bai, N. Zhang, Z. Lu, M. Zhu, Y. Wang, K. Jiang, Custom-tailoring tight [150] O. Karatas, R. Keyikoglu, N. Atalay Gengec, V. Vatanpour, A. Khataee, A review
nanocomposite membranes for advanced reclamation of hairwork dyeing on dendrimers in preparation and modification of membranes: progress,
effluent, J. Memb. Sci. 636 (2021), 119580, https://doi.org/10.1016/j. applications, and challenges, Mater. Today Chem. 23 (2022), 100683, https://
memsci.2021.119580. doi.org/10.1016/j.mtchem.2021.100683.
[127] Y. Li, X. You, Y. Li, J. Yuan, J. Shen, R. Zhang, H. Wu, Y. Su, Z. Jiang, Graphene [151] D.D. Shao, W.J. Yang, H.F. Xiao, Z.Y. Wang, C. Zhou, X.L. Cao, S.P. Sun, Self-
quantum dot engineered ultrathin loose polyamide nanofilms for high- cleaning nanofiltration membranes by coordinated regulation of carbon quantum
performance nanofiltration, J. Mater. Chem. A. 8 (2020) 23930–23938, https:// dots and polydopamine, ACS Appl. Mater. Interfaces. 12 (2020) 580–590, https://
doi.org/10.1039/d0ta09319j. doi.org/10.1021/acsami.9b16704.
[128] H. Sun, P. Wu, Tuning the functional groups of carbon quantum dots in thin film [152] S. Salehian, H. Heydari, M. Khansanami, V. Vatanpour, S. Abbas Mousavi,
nanocomposite membranes for nanofiltration, J. Memb. Sci. 564 (2018) 394–403. Fabrication and performance of polysulfone/H2O2-g-C3N4 mixed matrix
[129] J.Y. Gan, W.C. Chong, L.C. Sim, C.H. Koo, Y.L. Pang, E. Mahmoudi, A.W. membrane in a photocatalytic membrane reactor under visible light irradiation
Mohammad, Novel Carbon Quantum Dots / Silver Blended Polysulfone for removal of natural organic matter, Sep. Purif. Technol. 285 (2022), 120291,
Membrane with Improved Properties and Enhanced Performance in Tartrazine https://doi.org/10.1016/j.seppur.2021.120291.
Dye Removal, (n.d.). [153] K. Feng, L. Hou, B. Tang, P. Wu, A self-protected self-cleaning ultrafiltration
[130] B. Zhang, W. Wang, L. Zhu, N. Li, X. Chen, J. Tian, X. Zhang, Simultaneously membrane by using polydopamine as a free-radical scavenger, J. Memb. Sci. 490
enhanced permeability and anti-fouling performance of polyethersulfone (2015) 120–128.
ultrafiltration membranes by structural control and mixed carbon quantum dots, [154] L. Panzella, G. Gentile, G. D’Errico, N.F. Della Vecchia, M.E. Errico,
J. Memb. Sci. 641 (2022), 119931, https://doi.org/10.1016/j. A. Napolitano, C. Carfagna, M. d’Ischia, Atypical structural and π-electron
memsci.2021.119931. features of a melanin polymer that lead to superior free-radical-scavenging
[131] Z. Wei, Y. Yen, W. Chan, E. Mahmoudi, A. Wahab, H. Chieh, L. Ching, C. Hoon, properties, Angew. Chemie Int. Ed. 52 (2013) 12684–12687.
Journal of Water Process Engineering Preparation of a novel polysulfone [155] Y. Mi, N. Wang, X. Fang, J. Cao, M. Tao, Z. Cao, Interfacial polymerization
membrane by incorporated with carbon dots grafted silica from rice husk for dye nanofiltration membrane with visible light photocatalytic self-cleaning
removal, J. Water Process Eng. 40 (2021), 101805, https://doi.org/10.1016/j. performance by incorporation of CQD/TiO2, Sep. Purif. Technol. 277 (2021),
jwpe.2020.101805. 119500, https://doi.org/10.1016/j.seppur.2021.119500.
[132] J. Ahn, S. Pak, Y. Song, H. Kim, In-situ synthesis of carbon dot at cellulose [156] H. Zhang, J. Zhang, J. Luo, Y. Wan, A novel paradigm of photocatalytic cleaning
nanofiber for durable water treatment membrane with high selectivity, for membrane fouling removal, J. Memb. Sci. 641 (2022), 119859, https://doi.
Carbohydr. Polym. 255 (2021), 117387, https://doi.org/10.1016/j. org/10.1016/j.memsci.2021.119859.
carbpol.2020.117387. [157] S. Safa, M. Khajeh, A.R. Oveisi, R. Azimirad, H. Salehzadeh, Photocatalytic
[133] S. Singh, N. Shauloff, C.P. Sharma, R. Shimoni, C.J. Arnusch, R. Jelinek, Carbon performance of graphene quantum dot incorporated UiO-66-NH2 composite
dot-polymer nanoporous membrane for recyclable sunlight-sterilized facemasks, assembled on plasma-treated membrane, Adv. Powder Technol. 32 (2021)
J. Colloid Interface Sci. 592 (2021) 342–348, https://doi.org/10.1016/j. 1081–1087, https://doi.org/10.1016/j.apt.2021.02.013.
jcis.2021.02.049. [158] R.L.G. Lecaros, M.E. Bismonte, B.T. Doma, W.S. Hung, C.C. Hu, H.A. Tsai, S.
[134] H. Koulivand, A. Shahbazi, V. Vatanpour, M. Rahmandoust, Development of H. Huang, K.R. Lee, J.Y. Lai, Alcohol dehydration performance of pervaporation
carbon dot-modified polyethersulfone membranes for enhancement of composite membranes with reduced graphene oxide and graphene quantum dots
nanofiltration, permeation and antifouling performance, Sep. Purif. Technol. 230 homostructured filler, Carbon N. Y. 162 (2020) 318–327, https://doi.org/
(2020), 115895, https://doi.org/10.1016/j.seppur.2019.115895. 10.1016/j.carbon.2020.02.042.
[135] H. Koulivand, A. Shahbazi, V. Vatanpour, M. Rahmandoost, Novel antifouling and [159] P. Shao, R.Y.M. Huang, Polymeric membrane pervaporation, J. Memb. Sci. 287
antibacterial polyethersulfone membrane prepared by embedding nitrogen-doped (2007) 162–179.
carbon dots for efficient salt and dye rejection, Mater. Sci. Eng. C. 111 (2020), [160] R.L.G. Lecaros, K.Y. Chua, L.L. Tayo, W.S. Hung, C.C. Hu, Q.F. An, H.A. Tsai, K.
110787, https://doi.org/10.1016/j.msec.2020.110787. R. Lee, J.Y. Lai, The fine-structure characteristics and isopropanol/water
[136] H. Feng, J. Liu, Y. Mu, N. Lu, S. Zhang, M. Zhang, J. Luan, G. Wang, Hybrid dehydration through pervaporation composite membranes improved with
ultrafiltration membranes based on PES and MOFs @ carbon quantum dots for graphene quantum dots, Sep. Purif. Technol. 247 (2020), 116956, https://doi.
improving anti-fouling performance, Sep. Purif. Technol. 266 (2021), 118586, org/10.1016/j.seppur.2020.116956.
https://doi.org/10.1016/j.seppur.2021.118586. [161] R.L.G. Lecaros, R.E. Valbuena, L.L. Tayo, W.S. Hung, C.C. Hu, H.A. Tsai, S.
[137] N. Shaari, S.K. Kamarudin, R. Bahru, Carbon and graphene quantum dots in fuel H. Huang, K.R. Lee, J.Y. Lai, Tannin-based thin-film composite membranes
cell application: an overview, Int. J. Energy Res. 45 (2021) 1396–1424, https:// integrated with nitrogen-doped graphene quantum dots for butanol dehydration
doi.org/10.1002/er.5889. through pervaporation, J. Memb. Sci. 623 (2021), 119077, https://doi.org/
[138] V.C. Hoang, K. Dave, V.G. Gomes, Carbon quantum dot-based composites for 10.1016/j.memsci.2021.119077.
energy storage and electrocatalysis: mechanism, applications and future [162] R.L.G. Lecaros, A.R. Matira, L.L. Tayo, W.S. Hung, C.C. Hu, H.A. Tsai, K.R. Lee, J.
prospects, Nano Energy. 66 (2019), 104093, https://doi.org/10.1016/j. Y. Lai, Homostructured graphene oxide-graphene quantum dots nanocomposite-
nanoen.2019.104093. based membranes with tunable interlayer spacing for the purification of butanol,
[139] L. Wu, Z. Zhang, J. Ran, D. Zhou, C. Li, T. Xu, Advances in proton-exchange Sep. Purif. Technol. 283 (2022), 120166, https://doi.org/10.1016/j.
membranes for fuel cells: an overview on proton conductive channels (PCCs), seppur.2021.120166.
Phys. Chem. Chem. Phys. 15 (2013) 4870–4887. [163] Z. Xiong, L. Dai, Y. Wang, K. Qu, Y. Xia, L. Lei, K. Huang, Z. Xu, Two-dimensional
[140] T.J. Peckham, S. Holdcroft, Structure-morphology-property relationships of non- sub-nanometer confinement channels enabled by functional carbon dots for ultra-
perfluorinated proton-conducting membranes, Adv. Mater. 22 (2010) 4667–4690, permeable alcohol dehydration, J. Memb. Sci. 644 (2022), 120069, https://doi.
https://doi.org/10.1002/adma.201001164. org/10.1016/j.memsci.2021.120069.
[141] K.A. Mauritz, R.B. Moore, State of understanding of nafion, Chem. Rev. 104 [164] M. Wang, F. Pan, L. Yang, Y. Song, H. Wu, X. Cheng, G. Liu, H. Yang, H. Wang,
(2004) 4535–4586, https://doi.org/10.1021/cr0207123. Z. Jiang, X. Cao, Graphene oxide quantum dots incorporated nanocomposite
[142] W. Jia, B. Tang, P. Wu, Carbon dots with multi-functional groups and the membranes with high water flux for pervaporative dehydration, J. Memb. Sci.
application in proton exchange membranes, Electrochim. Acta. 260 (2018) 563 (2018) 903–913, https://doi.org/10.1016/j.memsci.2018.06.062.
92–100, https://doi.org/10.1016/j.electacta.2017.11.047. [165] M.Y. Lim, Y.S. Choi, J. Kim, K. Kim, H. Shin, J.J. Kim, D.M. Shin, J.C. Lee, Cross-
[143] A. Sarapuu, E. Kibena-Põldsepp, M. Borghei, K. Tammeveski, Electrocatalysis of linked graphene oxide membrane having high ion selectivity and antibacterial
oxygen reduction on heteroatom-doped nanocarbons and transition activity prepared using tannic acid-functionalized graphene oxide and
metal–nitrogen–carbon catalysts for alkaline membrane fuel cells, J. Mater. polyethyleneimine, J. Memb. Sci. 521 (2017) 1–9, https://doi.org/10.1016/J.
Chem. A. 6 (2018) 776–804. MEMSCI.2016.08.067.
[144] R. Narducci, E. Sgreccia, P. Knauth, M.L. Di Vona, Anion exchange membranes [166] H. Zeng, S. He, S.S. Hosseini, B. Zhu, L. Shao, Emerging nanomaterial
with 1D, 2D and 3D fillers: a review, Polymers (Basel). 13 (2021), https://doi. incorporated membranes for gas separation and pervaporation towards energetic-
org/10.3390/polym13223887.
21
efficient applications, Adv. Membr. 2 (2022), 100015, https://doi.org/10.1016/J. [169] H. Jiang, Z. Guo, H. Wang, X. Liu, Y. Ren, T. Huang, J. Xue, H. Wu, J. Zhang,
ADVMEM.2021.100015. Y. Yin, Z. Jiang, M.D. Guiver, Solvent-processable 0D covalent organic framework
[167] A. Ghadimi, S. Norouzbahari, V. Vatanpour, F. Mohammadi, An Investigation on quantum dot engineered composite membranes for biogas upgrading, J. Memb.
Gas Transport Properties of Cross-Linked Poly(ethylene glycol diacrylate) Sci. 640 (2021), 119803, https://doi.org/10.1016/j.memsci.2021.119803.
(XLPEGDA) and XLPEGDA/TiO2 Membranes with a Focus on CO2 Separation, [170] Y. Zhu, X. Zhang, L. Zhang, L. Hu, F. Zhang, Y. Wang, Y. Ding, X. Zhu, W. Yang,
Energy Fuels. 32 (2018), https://doi.org/10.1021/acs.energyfuels.8b00545. Membranes constructed with zero-dimension carbon quantum dots for CO2
[168] F. Shi, Q. Tian, J. Wang, Q. Wang, F. Shi, Y. Li, S.P. Nunes, Carbon quantum dot- separation, J. Memb. Sci. 664 (2022), 121086, https://doi.org/10.1016/j.
enabled tuning of the microphase structures of poly(ether-b-amide) membrane for memsci.2022.121086.
CO2separation, Ind. Eng. Chem. Res. 59 (2020) 14960–14969, https://doi.org/
10.1021/acs.iecr.0c03432.
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Separation and Purification Technology 326 (2023) 124876

Contents lists available at ScienceDirect

Separation and Purification Technology

Carbon-based quantum dots in fabrication and modification of membranes:

Fig. 3. Synthesis precursors and methods of CQDs.

Fig. 11. Cross-sectional SEM images of (a) homo-

CQDs that synthesized by hydrothermal method using CA and EDA References

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