Alexandria Engineering Journal

Multifunctional crosslinked chitosan/nitrogen-doped graphene quantum dot for

wastewater treatment
--Manuscript Draft--

Manuscript Number: AEJ-D-20-01825

Article Type: Short Communication

Keywords: Water treatment; Nanomaterials; Quantum dots

Corresponding Author: mohamed Abdel Khalek tahooon, Ph.D.

King Khalid University
Abha, Asir SAUDI ARABIA

First Author: Abdelfattah Amari

Order of Authors: Abdelfattah Amari

Basem Alalwan

Saifeldin M. Siddeeg

mohamed Abdel Khalek tahooon, Ph.D.

Norah Salem Alsaiari

Faouzi Ben Rebah

Abstract: The fabrication of multifunctional nanomaterial for the adsorption of different types of
pollutants is a challenge and could be a solution to many water treatment problems.
So, our current short article discusses a promising item, in which crosslinked
chitosan/nitrogen doped-graphene quantum dot nanocomposites (CS/NGQD)
synthesized using glutaraldehyde as cross-linker to remove several types of pollutants
includes bacteria, biomolecules, fluoride, dyes, and pharmaceuticals. The results
showed enhanced removal efficiency of the nanocomposites toward protein more than
its component parts. The enhanced results also obtained for the other pollutants
including bacteria, dyes, pharmaceuticals, and fluoride. The synthesis process of the
nanocomposite is cost-effective. However, more details are required for the application
of this nanocomposite for water treatment in large scale.

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Manuscript

Multifunctional crosslinked chitosan/nitrogen-doped graphene quantum

1
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3 dot for wastewater treatment
4
5
6 Abdelfattah Amari a, b, Basem Alalwana, Saifeldin M. Siddeeg c,d, Mohamed A. Tahoonc*, Norah Salem
7
8 Alsaiarid, and Faouzi Ben Rebahc,f
9 a
10 Department of Chemical Engineering, College of Engineering, King Khalid University, PO Box 9004, Abha
11 61413, Saudi Arabia
b
12 Research Laboratory: Energy and Environment, National School of Engineers, Gabes University, Gabes
13 6072, Tunisia
14
15 c
Department of Chemistry, College of Science, King Khalid University, P.O. Box 9004, Abha 61413, Kingdom
16 of Saudi Arabia
17
18 d
Chemistry and Nuclear Physics Institute, Atomic Energy Commission, P.O. Box 3001, Khartoum 11111, Sudan
19
20 e
Chemistry Department, College of Science, Princess Nourah Bint Abdulrahman University, Riyadh, Saudi
21
22 Arabia
23 f
24 Higher Institute of Biotechnology of Sfax (ISBS), Sfax University, P.O. Box 263, Sfax 3000, Tunisia
25
26 Abstract
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28
29 The fabrication of multifunctional nanomaterial for the adsorption of different types of
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32 pollutants is a challenge and could be a solution to many water treatment problems. So, our
33
34 current short article discusses a promising item, in which crosslinked chitosan/nitrogen
35
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37
doped-graphene quantum dot nanocomposites (CS/NGQD) synthesized using glutaraldehyde
38
39 as cross-linker to remove several types of pollutants includes bacteria, biomolecules,
40
41 fluoride, dyes, and pharmaceuticals. The results showed enhanced removal efficiency of the
42
43
44 nanocomposites toward protein more than its component parts. The enhanced results also
45
46 obtained for the other pollutants including bacteria, dyes, pharmaceuticals, and fluoride. The
47
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49 synthesis process of the nanocomposite is cost-effective. However, more details are required
50
51 for the application of this nanocomposite for water treatment in large scale.
52
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54 Keywords: Water treatment; Nanomaterials; Quantum dots
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56
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58 *Corresponding author E-mail address: tahooon_87@yahoo.com (Mohamed A Tahoon).
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60 Tel: +966552788212
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 1. Introduction
1
2 Clean water is essential for better life [1, 2]. So, fabrication of new materials for
3
4
5 water treatment is attracting the attention of researchers [3, 4]. The treatment of chitin
6
7 via strong alkaline medium led the formation of exceptional amino-polysaccharide
8
9
10 called chitosan (Cs). Crustaceans, insect exoskeletons, and fungal cell walls are the
11
12 main sources of chitosan natural polymers [5-7]. Today, good bioactive low cost
13
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15 natural polymers like Cs attract the attention of researchers in several applications
16
17 such as tissue and biomaterials engineering due to their large surface area,
18
19
biodegradability, biocompatibility, and non-toxicity [8]. But, chitosan applications
20
21
22 are limited due to some problems such as surface roughness, aqueous uncontrolled
23
24 swelling, fast degradation rate, and low mechanical properties. To overcome these
25
26
27 limitations chitosan polymers can be incorporated with nano-fillers such as graphene
28
29 quantum dot (GQD) or cross links via ionic and covalent crosslinking [9]. NH2
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32 groups of Cs bonded the cross linker such as glutaraldehyde (GA) to synthesize 3D
33
34 structure of improved swelling features, mechanical properties, and stability [10].
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37
GQD is carbonaceous zero dimensional nanomaterial results from graphene and
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39 carbon dots with width less than 20 nm. GQD is promising material for different
40
41 applications like antimicrobial materials, drug delivery, biosensors, and bio-imaging
42
43
44 due to their exceptional properties like biocompatibility, brilliant bioactivity, and
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46 high solubility in several solvents, low toxicity, noticed photostability, and high
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49 hydrophilicity [10, 11]. Also, they used for the water treatment applications with high
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51 efficiency [12] due to their edge effects and quantum confinement. More active sites
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54 for GQD can be provided via doping with heteroatom nitrogen or sulfur element [13].
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56 Thus, the polymeric composite can be richening with high number binding sites via
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combination with nitrogen-doped graphene quantum dot (NGQDs). The doping
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 process provides active chelating site by doing as dynamic electron donor. The
1
2 doping process improves the adsorption performance toward different contaminants
3
4
5 via several interactions such as electrostatic and hydrophobic interactions, π– π
6
7 stacking, and hydrogen bonding. So, N-free GQDs has less performance than
8
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10 NGQDs in pollutants removal. The solubility problems prevent the using of NGQDs
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12 alone for water treatment so, it is incorporated with polymeric matrix for better
13
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15 physicochemical characters and higher removal capacity of contaminants. This
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17 coupling of Cs and NGQDs provide a multifunctional nanomaterial with exceptional
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19
properties for the water treatment from several contaminants such as bacteria,
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22 pharmaceutical compounds, fluoride, and dyes. Thus, the novelty of this work is the
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24 fabrication of new nanocomposite with very simple and easy method for the
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27 elimination of several types of contaminants even bacteria.
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29 2. Experimental
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32 2.1. Chemicals
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35 Acros (New Jersey, USA) is the source of the used chitosan in this study with molecular
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37 weight of 600-800 x103 g/mol. All other used chemicals were supplied from Merck Co.,
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40 Germany.
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43 2.2. Synthesis of nitrogen-doped graphene quantum dot (NGQD)
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NGQD was synthesized according to the modified method of Achadu and Nyokong [14]
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49 by Qu et al. [15] in which the synthesis occurred via hydrothermal treatment of carbon
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51 source (citric acid) in the existence of nitrogen source (urea). 6 mL of distilled water was
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54 used to dissolve 3 mol of urea and 1 mol of citric acid that shacked until clear then heated
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56 for 7 h at 185 oC in Teflon tied stainless autoclave. The produced dark powder of NGQD
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 was then extracted by the addition of ethyl alcohol. Then the powder centrifuged and
1
2 dried in the normal temperature.
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6 2.3. Synthesis of Cs/ NGQD nanocomposite
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9 Solution casting method under sonochemistry was used for the synthesis of CCS/NGQD
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nanocomposite in which 8 mL of 1% citric acid was used for the dissolving of 0.1 g
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14 chitosan that then ultra-sonicated for 6 minutes. After that, 5 wt % of NGQD previously
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16 dissolved in water was added slowly with vigorous stirring for five hours to chitosan
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19 solution. Then the previous mixture was ultra-sonicated for half-hour followed by the
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21 addition of (GA, 10 wt %) with vigorous stirring up to 24 hours. The produced
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24 nanocomposite was dried and sinking for two hours in (NaOH, 2 wt %) to neutralize the
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26 dark brown nanocomposite.
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2.4. Nanocomposite characterization
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33 The synthesized nanomaterials were characterized using different techniques including
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35 FT-IR, XRD, SEM, TEM, and Raman spectroscopy. FT-IR of samples was performed
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38 using PerkinElmer Spectrum two spectrometer (United States). XRD was performed
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40 using Rigaku Ultima Diffractometer 1840 (Japan). Raman spectroscopic analysis was
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performed using T64000 Raman spectroscope. SEM analysis was performed using
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45 HITACHI S-4160 while TEM analysis was performed using Philips CM 120.
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48 2.5. Adsorption experiments
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52 Different pollutants were tested for removal using the synthesized nanomaterials. The
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54 examined pollutants included E.coli as example of bacteria, protein as example of
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biomolecules, pharmaceuticals included chlorothiazide, carbamazepine, and ranitidine,
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59 dyes included orange G, methylene blue, azo blue, and fluoride ions. The ability of
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 synthesized nanomaterials to remove proteins from water was studied using bovine
1
2 serum albumin that can cause many problems when released in wastewater while E. coli
3
4
5 was used as indication of synthesized nanomaterials ability to remove dangerous
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7 bacteria. Fluoride ions and previously mentioned dyes were removed by adding 0.12 g of
8
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10 synthesized nanomaterials with (11 mg/L, 100 mL) of pollutants containing aqueous
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12 solution under continuous shaking in incubator at 150 rpm for 185 minutes at 303.15 K
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15 and pH of 6 maintained using standard solutions of 0.1N sodium hydroxide and 0.1 N
16
17 hydrochloric acid. Fluoride ions and dyes removal efficiency (qe) was calculated using
18
19
Eq.1. Also, the removal efficiency of pharmaceuticals was calculated using the same
20
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22 equation via UV-vis spectroscopy in which chlorothiazide measured at 293 nm,
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24 carbamazepine measured at 286 nm, and 313 nm for ranitidine. For pharmaceuticals
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27 removal, the same optimized conditions used for dyes and fluoride removal were used
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29 except the pharmaceutical concentration was 50 mg/L.
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32
𝑉[𝐶𝑖 − 𝐶𝑡 )/𝐶𝑖 ]
33 𝑞𝑒 = [1]
34 𝑊
35
36
37 Where W denotes the weight of pollutant used and V denotes its volume. Also, Ci
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denotes the initial pollutant concentration and Ct denotes its concentration after the
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42 experimental time. For the bacterial removal, the adsorbent dose was 0.42 g with initial
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44 bacterial load of 7 x 106 per one mL of water which incubated with shaking at pH of 6 for
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47 185 minutes at 303.15 K. Spread plate counting and standard serial dilution methods
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49 were used for E. coli load determination in the solution. Bacterial removal efficiency
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52 (RE) was determined according to Eq.2.
53
54
55 𝑁𝑖 − 𝑁𝑡 )
56 𝑅𝐸 (%) = × 100 [2]
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𝑁𝑖
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 Where Ni denotes the initial E. coli load and Nt denotes its load after the mentioned
1
2 experimental time. For serum albumin removal the same conditions for bacterial removal
3
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5 were used with (500 mg/L of protein, 100 mL). The albumin removal efficiency (RE)
6
7 was calculated using Eq.3.
8
9
10
𝐶𝑖 − 𝐶𝑡 )
11 𝑅𝐸 (%) = × 100 [3]
12 𝐶𝑖
13
14
15 Where Ci denotes the albumin initial concentration and Ct denotes its concentration after
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18 experimental time.
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21 3. Results and discussion
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24 3.1. Nanomaterials characterization
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27 The XRD of CS, NGQD, and CS/ NGQD is shown in Fig.1a. According to XRD of
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29 NGQD, there is a broad peak at 2theta= 22 that represents hexagonal graphite plane of
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32 (002) and may be belonged to the NGQD surface defects or to reduced oxygen produced
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34 via doping process. The total carbonization of citric acid to NGQD was indicated from
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37 the absence of citric acids peaks. The crystallinity of combined CS decreases than pure
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39 one at 19.8o due to the cross-linking with glutaraldehyde that destroyed the regularity of
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pure CS via breaking the intra-molecular and inter-molecular hydrogen bonds as reported
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44 in literature [16]. But, herein the combined CS crystallinity is more decreased than
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46 expected that may related to glutaraldehyde low concentration. As shown in XRD pattern
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49 the addition of quantum dots to CS led to the existence of the same peaks like CS with
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51 small shift of characteristic peak to upper angle equal to 20.8o that related to electrostatic
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54 attractions and H-bonds between CS chains and doped quantum dots. Raman shift was
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56 used to explore the combination between CS and NGQD as shown in Fig1b. According
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to the spectra there is two characteristic wide bands of NGQD at 1370 and 1590 cm-1.
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 The two bands are corresponding to breathing mode from sp3 defects and E2g mode from
1
2 vibration of bonded sp2 carbons, respectively. The red shift of the first peak to lower
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5 value 1360 cm-1 was observed after the addition of NGQD over CS polymer as well as it
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7 becomes more eminent. The ratio of two characteristic bands intensities was used to
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10 assess the structural defects. This ratio was found to equal 0.74 and 0.62 for CS/NGQD
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12 and NGQD, respectively. As noticed this ratio increased after interaction between CS and
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15 NGQD due to H-bonds between two materials and also, a decrease in the number of
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17 oxide functional groups resulted from nucleophilic substitution between NGQD and CS
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sites.
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25 1360 1592
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27 CS/NGQD
28 CS/NGQD
Transmittance (%)

29 1590
Intensity (a.u.)

30 CS
31 1370
32 3428 1641 1459
33
1077
34 NGQD
3435 NGQD
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37 (b)
38 (a)
2930 1573 1385
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40 3500 3000 2500 2000 1500 1000 500 1350 1400 1450 1500 1550 1600 1650 1700
41 -1
Wavenumber (nm) Raman shift (cm )
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 1
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21 Fig.1. FT-IR (a), Raman shift (b), and XRD (c) of nitrogen doped graphene quantum
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23 dot, chitosan, and nitrogen doped graphene quantum dot/chitosan nanocomposite.
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FT-IR spectra of CS, NGQD, and CS/NGQD are shown in Fig.1c. According to the
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28 spectrum of CS, bands at 1384, 1422, and 1599 cm-1 are corresponding to CH
29
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31 symmetrical bending vibration, CH2 bending, and NH bending, respectively while CH
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33 stretching vibration, OH and NH2 stretching vibrations are represented by 2920, 2861,
34
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and 3421 cm-1 bands, respectively. The band at 1654 cm-1 represents C=O stretching of
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38 amide. The cross-linking reaction between CS and aldehyde of glutaraldehyde produced
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40 an imine group represented by peak at 1641 cm-1 corresponding to C=N bond vibrations.
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43 Also, there is no band at 1720 cm-1 that belongs to free aldehyde due to the low
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45 glutaraldehyde concentration in chitosan. According to the spectrum of NGQD, C=O and
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48 CN bond stretching vibrations are represented by bands at 1651 and 1418 cm-1,
49
50 respectively. COO- occurring on the boundaries of the NGQDs asymmetric and
51
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53 symmetric stretching vibrations is represented by peaks at 1385 and 1573 cm-1. Peaks at
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55 2858 and 2931 cm-1 represents asymmetric and symmetric stretching vibrations of CH
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58 bond. OH- and NH- stretching vibrations are represented by the wide band at 3100–3500
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60 cm−1. FT-IR spectrum of NGQD reveals no characteristic bands of aromatic ring.
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 According to FT-IR spectrum of CS/ NGQD nanocomposite, all bands of NGQD and CS
1
2 were represented with small difference in the intensity. Additionally, there was a red shift
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5 of bands at 1599 and 3453 cm-1 corresponding to NH2 and OH groups to 1597 and 3429
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7 cm-1. These deviations were due to the CS and NGQD functional groups combination via
8
9
10 hydrogen bonding. Additionally, SEM and TEM images of synthesized materials were
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12 performed and shown in Fig.2 for more characterization. According to SEM image of CS
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15 (Fig.2a) and CS/NGQD nanocomposite (Fig.2b), there is a clear difference in the surface
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17 morphology before and after loading the NGQD to CS. CS has a rubble-like structure
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according to its SEM image. SEM image of CS/NGQD nanocomposite have small
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22 ruptures and cracks providing higher effective area for contaminants capturing. TEM
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24 image of CS/NGQD nanocomposite (Fig.2c) shows a well distributed quantum dots over
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27 the chitosan matrix.
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 Fig.2. SEM image of CS (a), CS/NGQD (b) and TEM image of CS/NGQD (c)
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3 3.2. Adsorption studies
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7 Protein removal efficiency using synthesized nanomaterials presented in Fig.3a indicated
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9 that CS removed 16% of protein while NGQD removed 45%. After the accumulation of
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doped quantum dot over polymer matrix 60% of protein was removed indicating an
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14 enhanced efficiency. Additionally, the CS/NGQD nanocomposite showed enhanced
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16 bacterial removal than CS and NGQD. The nanocomposite removed 88% of initial
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19 bacterial load as shown in Fig. 3a while CS only removed 19% and NGQD removed
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21 80%. Another type of contaminants that must be controlled powerfully is
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24 pharmaceuticals. The synthesized nanomaterials were tested here for the removal of three
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26 drugs as mentioned in experimental section. As shown in Fig. 3b, the three drugs can be
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removed by the CS, NGQD, and CS/NGQD nanocomposite. But, the CS/NGQD
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31 nanocomposite showed higher abilities for drugs removal than uncombined counterparts.
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33 This high removal efficiency of nanocomposite is related to higher active site to chelate
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36 pollutants as well as improved swelling properties than uncombined counterparts that
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38 efficiently affects the surface area of nanomaterial.
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46 100
14
Protein Ranitidine
47 Bacteria Carbamazepine
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48 Chlorothiazide
Removal Effeciency (mg/g)
Removal Effeciency (%)

80
49 10
50 (b)
60 8
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52 (a)
6
40
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54 4
20
55 2
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57 0 0
CS NGQD CS/NGQD CS NGQD CS/NGQD
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 1
2 120 Azo blue
3 Methylene blue

Removal Effeciency (mg/g)

100 Orange G
4 Flouride
5 80
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7 60 (c)
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40
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10 20
11
12 0
13 CS NGQD CS/NGQD
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16 Fig.3. Multiple contaminants removal efficiency using synthesized materials; (a) removal
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19 of bacteria and protein, (b) removal of pharmaceuticals, and (c) removal of fluoride and
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21 dyes
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25 Moreover, the synthesized nanomaterials were tested for the removal of number of dyes
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27 and fluoride as shown in Fig.3c. After the adsorption experiment, the residual dyes and
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fluoride was monitored to get the removal efficiency. As data show in Fig.3c, the
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32 CS/NGQD has the better removal efficiency for all dyes and fluoride than CS and NGQD
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34 meaning the improved surface properties by loading the doped quantum dots over
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37 chitosan support. The results obtained in this study are challenged with the other
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39 prepared materials for the water/wastewater treatment especially it is multifunctional
40
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42 nanocomposite used for the removal of different types of pollutants. However, additional
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44 details are required such as thermodynamic parameters [17-22] of adsorption and
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adsorption isotherm to enhance the application of CS/NGQD nanocomposite for the large
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49 scale water treatment. The results in current study indicate that this fabricated
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51 nanocomposite is promising for water treatment.
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55 4. Conclusion
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 This work indicates that the synthesized CS/NGQD has the ability to remove several
1
2 types of pollutants (organic and inorganic) from water which make it a promising
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4
5 material for wastewater treatment. Additionally its cost-effective properties and
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7 exceptional superiority enhance its application for adsorption of hazard pollutants from
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10 water. Its ability to remove different types of contaminants with high efficiency makes it
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12 useful for industrial wastewater treatment. But, ability to use this nanocomposite for
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15 wastewater treatment in large scale still required more details.
16
17
18 Declaration of Competing Interest
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21 The authors declare no conflict of interest.
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23
24
25 Acknowledgments
26
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28 The authors extended their appreciation to the Deanship of Scientific Research at King
29
30 Khalid University for funding this work through General Research Project under grant
31
32
33 number (G.R.P-316-40). Also, this research was funded by the Deanship of Scientific
34
35 Research at Princess Nourah bint Abdulrahman University through the Fast-track
36
37
38 Research Funding Program.
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41 References
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47 materials and wastewater as growth media for microbial bioflocculants
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Title Page

Multifunctional crosslinked chitosan/nitrogen-doped graphene quantum

dot for wastewater treatment

Abdelfattah Amari a, b, Basem Alalwana, Saifeldin M. Siddeeg c,d, Mohamed A. Tahoonc*,

Norah Salem Alsaiarid, and Faouzi Ben Rebahc,f

a
Department of Chemical Engineering, College of Engineering, King Khalid University, PO
Box 9004, Abha 61413, Saudi Arabia
b
Research Laboratory: Energy and Environment, National School of Engineers, Gabes
University, Gabes 6072, Tunisia
c
Department of Chemistry, College of Science, King Khalid University, P.O. Box 9004, Abha
61413, Kingdom of Saudi Arabia
d
Chemistry and Nuclear Physics Institute, Atomic Energy Commission, P.O. Box 3001,
Khartoum 11111, Sudan
e
Chemistry Department, College of Science, Princess Nourah Bint Abdulrahman University,
Riyadh, Saudi Arabia
f
Higher Institute of Biotechnology of Sfax (ISBS), Sfax University, P.O. Box 263, Sfax 3000,
Tunisia

*Corresponding author E-mail address: tahooon_87@yahoo.com (Mohamed A Tahoon).

Tel: +966552788212
Conflict of Interest

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: