El‑Sayed et al.

BMC Chemistry (2023) 17:117 BMC Chemistry

https://doi.org/10.1186/s13065-023-01035-9

RESEARCH Open Access

Sustainable grafted chitosan‑dialdehyde

cellulose with high adsorption capacity of heavy
metal
Essam S. Abd El‑Sayed1, Sawsan Dacrory1, Hisham A. Essawy2, Hanan S. Ibrahim3, Nabila S. Ammar3 and
Samir Kamel1*

Abstract
A novel adsorbent was prepared using a backbone comprising chemically hybridized dialdehyde cellulose (DAC)
with chitosan via Schiff base reaction, followed by graft copolymerization of acrylic acid. Fourier transform infra‑
red spectroscopy (FTIR) confirmed the hybridization while scanning electron microscopy (SEM) revealed intensive
covering of chitosan onto the surface of DAC. At the same time, energy dispersive X-ray (EDX) proved the emer‑
gence of nitrogen derived from chitosan. The X-ray diffraction (XRD) indicated that the crystallinity of the backbone
and graft copolymer structures was neither affected post the hybridization nor the grafting polymerization. The
adsorbent showed high swelling capacity (872%) and highly efficient removal and selectivity of ­Ni2+ in the presence
of other disturbing ions such as ­Pb2+ or ­Cu2+. The kinetic study found that the second-order kinetic model could
better describe the adsorption process of ­(Cu2+, ­Ni2+) on the graft copolymer. In contrast, the first-order kinetic model
prevails for the binary mixture ­(Pb2+, ­Ni2+). Moreover, the correlation coefficient values for the adsorption process
of these binary elements using Langmuir and Freundlich isotherms confirmed that the developed grafted DAC/
chitosan exhibits a good fit with both isotherm models, which indicates its broadened and complicated structure.
Furthermore, the grafted DAC/chitosan exhibited high efficient regeneration and high adsorption capacity for ­Pb2+,
­Cu2+ and ­Ni2+.
Keywords Dialdehyde Cellulose, Chitosan, Grafting, Heavy Metal Ions Removal

Introduction possesses a cycloaliphatic structure that comprises both

Chitosan is a material from crustacean shells and is active amino and hydroxyl groups. Due to its inferior
usually wasted in seafood industries. Therefore, it can mechanical properties, chitosan can be crosslinked by
be applied as a suitable biopolymer in manufactur- several reagents, among which are glutaraldehyde [4–6],
ing blended or composite materials [1–3]. Chitosan formaldehyde [7, 8], and sulfuric acid [9, 10]. Because it
has numerous chelation sites, amino and hydroxyl groups
that adsorb the metal ions via coordination bonds or ion
*Correspondence:
Samir Kamel exchange, and multiple chelation sites, chitosan is a great
[email protected] choice for adsorbing the hazardous metal ions from an
1
Cellulose and Paper Department, National Research Centre,
aqueous solution. Therefore, numerous researchers have
Dokki 12622, Cairo, Egypt
2
Department of Polymers and Pigments, National Research Centre, looked at how chitosan and its modified forms’ capac-
Dokki 12622, Cairo, Egypt ity for adsorption can be employed to remove different
3
Department of Water Pollution, National Research Centre, Dokki 12622,
heavy metals [11]. In one attempt, He et al. studied the
Cairo, Egypt
removal of ­Cu2+ and ­Ni2+ by amidoxime-functionalized

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El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 2 of 15

chitosan, and it was found that the adsorption capac- Interestingly, the high aspect ratio of DAC renders it
ity was a function of initial concentration, pH solution, more liable and easier for efficient modification, espe-
coexisting ions, and process temperature [12]. The effect cially in the presence of a huge number of hydroxyl
of coexisting cations, including ­Na+, ­Ca2+, and ­Fe3+, on groups on the surface, presenting a unique functionaliza-
the adsorption of C ­ u2+ onto chitosan-grafted maleic acid tion platform [23]. This is mainly achieved by conferring
composite was clarified by another investigation. It was new groups on the surface while keeping the integrity of
found that the presence of F ­ e3+ significantly impacted the crystalline core unchanged [24, 25].
the efficiency of the adsorption process. This effect may Among the significant uses of chitosan and cellulose is
be attributed to the development of hydroxyl-Fe-coated their employment as backbones for grafting polymeriza-
chitosan-grafted maleic acid that intercalates ­Cu2+. The tion [26–28]. Cellulose was combined previously with
rivalry between C ­ u2+ and the interfering cations (­Na+ chitosan using different linking agents such as urea–
2+
and ­Ca ) for the negative adsorption sited on the surface formaldehyde-sulphuric acid [28], 3-methyl glutaric
of chitosan-grafted maleic acid, on the other hand, pro- anhydride [29], and Schiff base crosslinking [30]. Fur-
duced a reduction in the ­Cu2+ adsorption capacity. Addi- thermore, the applicability of chitosan-cellulose hybrids
tionally, the shielding of ­Cu2+ caused by the increase in as precursors for the fabrication of superabsorbent mate-
cations near the composite surface lowers the effective- rials was presented before [30–33].
ness of adsorption [13]. In continuation of these efforts, superabsorbent mate-
Further, cellulose, the most widely available organic rials were prepared via the grafting polymerization of
biopolymer in nature, is traditionally a high molecular acrylic acid on a backbone incorporating dialdehyde cel-
weight complicated structure with long chains of d-glu- lulose (DAC), chemically hybridized with chitosan. The
cose units linked with each other via β-1,4-glucosidic potential of the resulting material to reveal remarkable
bonds. It is non-toxic, renewable, biodegradable, and sorption selectivity during the adsorption of heavy metal
modifiable to have great potential as an excellent indus- ions with known removal difficulty, such as nickel, will be
trial material [7, 14]. The excellent properties of cellulose explored in the current work, particularly in the presence
are motivating researchers to undergo intensive efforts as of other confusing ions like lead and copper. Also, kinet-
a step on the way to develop novel hybridized biopoly- ics and isotherms were studied to understand the mecha-
meric structures with outstanding properties, especially nism of adsorption.
by combining/blending with other materials to remove
organic and inorganic pollutants from wastewater [15– Materials and methods
18]. Among the different available forms of cellulose, oxi- Materials
dized cellulose is the functionalized cellulose derivative Bagasse bleached pulp was obtained from Quena Com-
with high reactivity and is nontoxic, biodegradable, and pany of Paper Industry, Egypt, as a raw material. The
biocompatible. Selective cellulose oxidation is a robust chemical composition of the pulp was defined according
method of modification to give high-performance cel- to Tappi standards with cellulose content (96%), hemicel-
lulose-based materials for many applications, including lulose (3%), and very low lignin content. Chitosan, with
environmental, energy, smart materials, biomedical engi- a deacetylation degree > 90%, was supplied from Oxford
neering and healthcare, barrier applications, and active Laboratory, India. Sodium periodate was obtained from
food packaging [19]. Periodate oxidation of cellulose is a Analytical Rasayan, India. Acrylic acid was provided
reaction system that cleaves the C2–C3 bonds in mono- from Sigma-Aldrich, USA. In addition, N,N-methylene
mer units and oxidizes the vicinal hydroxyl groups into bisacrylamide (MBA) was ordered from Acros Organ-
2,3 dialdehyde moieties, dialdehyde cellulose (DAC). The ics, USA. All other chemicals in this study were analytical
advantage of this process is the possibility of further dial- grade and used without further purification.
dehyde oxidation into carboxylic ones [20, 21].
Moreover, its hydrophilicity, which the copious Preparation of dialdehyde cellulose (DAC)
hydroxyl groups provide, makes it attractive to many The dialdehyde cellulose (DAC) was prepared using a
researchers [22]. A material with such exciting features previously described procedure [34]. Briefly, 10 g cel-
can greatly provoke a dramatic change in the emergence lulose was poured into 100 mL of deionized water and
of highly valued materials for different applications. stirred to get a homogenized suspension. Then, 16 g of
Functionalization of DAC can expand its applications’ sodium periodate was added to the cellulose suspension,
fields and make it easier to be involved in constructing of the pH was adjusted to 3 using 1 M sulfuric acid solution,
crosslinked network structures. This is a promising way and the stirring continued in darkness at room tempera-
to obtain new soft materials with superior properties and ture for 24 h. Next, excess ethylene glycol was added to
multifunctional ability [23]. quench the reaction and ensure the decomposition of the
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 3 of 15

remaining periodate. The oxidized product, DAC, was Holland, was used to examine the different samples’ mor-
precipitated by pouring the solution into a significant phological aspects without coating.
excess of ethanol, which was washed several times alter-
natively with ethanol and water [35]. Finally, the product Water uptake
was filtrated and dried in an oven overnight at 60 °C. The water uptake of the formed superabsorbent was
determined gravimetrically using a dry piece by immer-
Preparation of DAC/chitosan hybrid sion in distilled water for 24 h to allow complete swell-
Chitosan (5 g) was dissolved in a 125 mL hydrochloric ing at room temperature. The swollen piece was removed
acid solution (0.5 M). Different weight ratios of DAC and wiped gently between two filter papers. The water
to chitosan (1:1, 1:2, and 1:3wt/wt) were employed and uptake (%) was then calculated as an average of three
stirred at 50 °C for 2 h afterward; the resulting slurry measurements using the following equation [37]:
was washed several times using ethanol before drying at
(M2 − M1)
room temperature [34]. Water Uptake% = X100
M1
Preparation of superabsorbent where; ­M1 and ­M2 are the dry and wet weights of the
As the initial step for preparing a superabsorbent, the superabsorbent, respectively.
DAC/chitosan hybrid, formulated with 1:2, was selected
as a backbone for completing the grafting polymerization Adsorption of heavy metal ions
of acrylic acid due to its superior handling concerning Batch adsorption experiments were performed by mixing
the other ratios in the sense that it was coherent and not 0.1–0.15 g of the superabsorbent with 100 mL of binary
brittle due to the reinforced structure. Thus, the supera- solutions, pre-adjusted at pH 5.6, incorporating 10 mg/L
bsorbent was prepared by charging various weight ratios for each element of the metal ions; ­ (Pb2+/Ni2+) and
of acrylic acid: 3:1, 6:1, and 9:1 with respect to the DAC/ 2+ 2+
­(Cu /Ni ). The binary systems were shaken at 150 rpm
chitosan hybrid. The mixture was dispersed in distilled
tures were filtered using filter papers (­Whatman®, No.
for 120 min at room temperature. After that, the mix-
water in a round flask, followed by the addition of potas-
sium persulphate (KPS) as an initiator (0.2 g) and meth- 3). Then, the metal ions concentration was determined in
ylene bisacrylamide (MBA) as a crosslinker (0.1 g). The the filtrate by inductive coupled plasma optical emission
reaction mixture was kept in a water bath at 60 °C under spectrometry (Agilent ICP-OES 5100, Australia) accord-
continuous stirring at 500 rpm for 1 h. Next, the pro- ing to a standard method, designed for examination of
duced graft copolymers, symbolized as H1, H2, and H3, water/wastewater [38]. Wavelength and operating con-
were washed with excess water and then used ethanol to ditions were; RF power = 1.3 kW—Plasma gas flow = 15
remove the excess water [36]. Finally, the grafted prod- ­Lmin−1—Auxiliary Ar, 0.2 ­ Lmin−1—Nebulizer Ar, 0.8
ucts were dried at 60 °C in the oven. The grafting per- −1
­Lmin —Pump rate, 1.5 ­ mLmin−1—Readings/replicate
centage (G %) was calculated by the following equations: 3—Wavelength, Cu, Ni, and Pb 324.752, 231.604, and
Wf − Wi 220.353 nm, respectively. The presented data represent
G% = X100 the average value of three readings.
Wi
where Wf and Wi are the weight of the DAC/chitosan Adsorption kinetics and isotherms
after and before the grafting polymerization, respectively. The kinetics and isotherms statistics assessment is crucial
The G% of H1, H2, and H3 were 235, 273, and 301, to explore the mechanism of the sorption reaction and
respectively. the type of interaction between the sorbate and adsor-
bent, respectively. Therefore, the adsorption kinetics was
Characterizations studied using pseudo-first-order and pseudo-second-
Fourier transform infrared spectroscopy (FTIR) was per- order, while the adsorption isotherms were controlled
formed on KBr discs of the samples using a Shimadzu using Langmuir and Freundlich models [39].
8400 S FT-IR spectrophotometer, and the relevant spec-
tra were recorded in the range of 400–4000 ­cm−1. X-ray Desorption studies
diffractograms were collected for the samples at 25 °C The typical batch sorption process of 0.1 g of sorbent
using a Diano X-ray diffractometer (XRD) equipped with in 100 mL of 10 mg/L binary solution ­(Pb+2, ­Ni+2) and
a monochromatic Cu Kα radiation source (λ = 0.154 nm, ­(Cu+2, ­Ni+2) was operated at the optimum operating con-
2θ = 5: 70°) over a scanning time of 5 min. An environ- dition. Then, the mixture was filtered through filter paper
mental scanning electron microscope (SEM), Quanta-250 (No. 41), and the filtrate concentration was analyzed.
fitted with EDX unit, FEI IN SPECTS Company, Philips, The loaded sorbent was placed in 100 mL of 0.1 M HCl
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 4 of 15

Scheme 1 Schematic representation of superabsorbent hydrogel

and stirred for 2 h to elution the ions from the sorbent, Structural characterization of the hydrogel
­(Pb+2, ­Ni+2) and ­(Cu+2, ­Ni+2) ions at room temperature. FT‑IR analysis
After filtration, the sorbent was washed with deionized The FTIR spectrum of the prepared cellulose nanofib-
water; the pH was adjusted using 0.1 M KOH to 6, fil- ers is presented in Fig. 1. As expected, the bands at
tered, washed with deionized water then the sorbent was 3450–3389 and 1021 ­cm−1 are dominant and refer to
employed for the next cycle. the stretching vibrations of the OH and C-O groups,
respectively. In addition, the OH bending appears in the
1520–1648 ­cm−1 region. The broadness of this band can
Results and discussion be justified by the adsorbed water, which is known to
Cellulose was surface-functionalized and offered high be strongly interacting with cellulosic chains. The peaks
adsorption efficiency toward different heavy metals. at 2826 and 2960 ­cm−1 represent asymmetric and sym-
As a result of its ability to target the vicinal secondary metric vibrations of ­CH2 groups, while the peak at 1370–
hydroxyl groups at C2 and C3 and cleave the C2-C3 bond 1395 ­cm−1 represents the scissoring motion of C ­ H2 [31].
in the anhydroglucose structural unit, sodium periodate The band of C–O–C, which indicates the pyranose ring
is a highly selective cellulose oxidant that produces two stretching vibration in cellulose, is centered at 1048 ­cm−1,
vicinal aldehyde groups (dialdehyde cellulose, DAC). while another peak, centered at 788 ­cm−1, is ascribed to
The procedure occurs in the dark, at an acidic pH of 3, the β-glycosidic linkages of cellulose. Also, the peak at
and at temperatures close to room temperature [35]. 1130 ­cm−1 presents the C–C ring stretching. The absence
Accordingly, the present study proposes a novel route to of a distinct characteristic peak around 1720–1740 ­cm−1
synthesize highly metal-adsorbed hydrogel (Scheme 1). confirms that all the lignin and hemicellulose have gone
Specifically, cellulose was oxidized by ­NaIO4to yield DAC through successive chemical treatments [42].
[40]. The Schiff-base reaction between the dialdehyde The spectrum of DAC shows the emergence of an influ-
groups on oxidized cellulose and the glucosamine groups ential band at 1740 ­cm−1, corresponding to the inser-
of chitosan leads to the formation of the crosslinking tion of the aldehydic carbonyl groups. Interestingly, this
network. Additionally, the superabsorbent hydrogel was emergence is associated with the broadening and shift
formed by the radical polymerization reaction using of the band centered at 1642 ­cm−1 along with complete
potassium persulfate as an initiator, which is soluble in flattening and collapse of the band in the region around
water and does not form alkoxide radicals, so it is the 3340–3555 ­cm−1, which confirms that aldehyde group
best radical initiator for hydrogen abstraction [41]. It was insertion took place on the OH groups [43].
used for hydrogen abstraction of the primary OH groups The relevant FTIR spectrum of chitosan shows a broad
in cellulose and/or chitosan transformed into radicals overlapping peaks at 3354 and 3291 ­cm–1, allotting the
which initiated graft polymerization of acrylic acid onto OH and ­NH2 frequencies of chitosan, together with a
DAC/Chitosan. peak at 1638 ­cm–1, assigning the amidic C = O and the
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 5 of 15

Fig. 1 FTIR spectra of; cellulose, chitosan, DAC/chitosan, and grafted DAC/chitosan

primary ­NH2 of chitosan. The C–O stretching of the pri- of many carbonyl environments and C = C derived from
mary alcoholic groups is revealed by a significant band lignin and/or hemicellulose. This also reveals these com-
at 1375 ­cm–1. Also, a peak at 1025 ­cm–1 corresponding ponents’ participation in the hybridization process with
to amino groups of glucosamine units can be observed chitosan.
together with a peak at 896 ­ cm–1 ascribed to C–N The graft copolymerization of acrylic acid on the
stretching. The absorption peak at 1063 ­cm–1 is attrib- DAC-chitosan backbone yielded an unequivocal band at
uted to C–O glucose bending, while those at 1419 and 2945 ­cm−1, attributed to the asymmetric and symmetric
1476 ­cm–1 describe the C–H bending of—CH2OH [32]. vibrations of C
­ H2 groups from the incorporated acrylic
The DAC-chitosan hybrid is characterized by a fall acid. In contrast, the carboxyl groups of acrylic acid are
down of the aldehydic carbonyl intensity and almost dis- recognized by the appearance of a band at 1720 ­cm–1 and
appearance of the band at 1638 ­cm–1, which is assigned a broadened band around 2515–2748 ­cm−1 [44].
to the primary ­NH2 of chitosan. This is evidence that the
hybridization proceeds principally via a Schiff base reac- XRD investigation on the prepared superabsorbent
tion between the aldehyde groups of DAC and amino X-ray diffraction (XRD) was performed to check the
groups of the chitosan. In addition, this can be further crystallinity of cellulose, chitosan, and grafted DAC/
corroborated by the small peaks at 1412 and 2144 ­cm–1, chitosan (Fig. 2). Several diffractions can be observed at
which refer to C-N and C = N bonds, respectively. 14.9°, 21.97°, and 26.5°, which are typical of both chitosan
Moreover, the ill-identified nature of the band beyond and DAC [32]. These patterns indicate that neither the
3000 ­cm–1 further supports this assumption. Finally, chemical hybridization between DAC and chitosan nor
it is worth noting broadband extended from 1640 to the graft copolymerization caused alteration of the crys-
2140 ­cm–1, which is thought to combine the overlapping talline skeleton of the main components.
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 6 of 15

Fig. 2 XRD spectra of; cellulose, chitosan, and grafted DAC/chitosan

Surface morphology and elemental composition pillars of this structure. This corroborates the growing of
for the hydrogels the graft polymer chains from the surface of the fibers,
Figure 3 displays the SEM micrographs of the obtained and the interactions between the chains are responsible
cellulose fibers, chitosan, DAC, DAC/chitosan, and the for the observed mechanical integrity.
obtained superabsorbent after the grafting polymeriza-
tion of acrylic acid. Successful preparation of DAC with Swelling studies of hydrogels
a diameter range from 5 to 15 µm and a length of sev- Increasing the feed monomer in grafting polymerization
eral hundred micrometers is ensured. The correspond- is generally approved to increase the grafted amount. The
ing EDX profile for these fibers revealed that carbon swelling of the hybrid structures was studied as a func-
(47.29%) and oxygen (52.71%) are the major components tion of time (1 h 10 days) and pH (3–12) (Fig. 5). All
of these structures. On the other hand, the chitosan structures followed the same trend: the water absorp-
appeared in around 8-µm thick flakes with a diameter tion level continuously increased with time and pH.
of 95–120 µm. After chemical coupling between DAC Figure 5 indicates that the amount of grafted acrylic
and chitosan, the surface of the fibers became smoother, acid in the DAC/chitosan hybrid backbone significantly
indicating that the ongoing reaction has proceeded via impacts water absorption with time. H3 acquired the
coating with the chitosan, which is additionally proved highest water absorption (872%) within 3 h of immer-
by the increased thickness indicating the chitosan, while sion in water. Thus, the samples can be sorted according
in the soluble state accumulated on the surface of DAC to their water absorption level at equilibrium in the order
Fibers. This was further confirmed by the relevant EDX H3 > H2 > H1, with 591% and 222% maximum absorption
(Fig. 4), from which it is apparent that a marked change levels for H2 and H1, respectively.
in the components’ percentages took place; the carbon Figure 5 shows the effect of pH on the swellability
level dropped to 36.67%, and the oxygen level changed of hydrogels, and it was found that H3 exhibited the
to 56.6%, whereas the nitrogen element has emerged highest absorption level over the whole pH range, fol-
with a level of 6.76%, which ensures the chemical link- lowed by H2. At the same time, H1 acquired the lowest
ing between chitosan and DAC. After copolymerization swelling value among these structures. At pH 12, the
on this hybridized backbone with acrylic acid, the cor- swelling ratio reached 950% for H3, 900% for H2, and
responding micrograph of the obtained superabsorbent declined to 700% for H1. The least water absorption
shows a porous structure. The relevant EDX analysis on was observed at pH 3, where all structures acquired
the superabsorbent demonstrated a drop of the nitrogen a close value of around 150%. The hybrid structures
content to 4.63%, which proves the graft copolymeriza- swelled systematically over the pH range from 3 to 12,
tion reaction. The superabsorbent structure is robust, with the superiority always in the H3 > H2 > H1 order.
while the hybridized fibers constitute the supporting
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 7 of 15

Fig. 3 SEM of cellulose, DAC, chitosan, DAC/chitosan, and grafted DAC/chitosan

It is clear from the effect of time and pH on the hydro- Sorption study
gel swellability that H3 has maximum absorption levels In its pure form, cellulose is a weak adsorbent to metal
over H1 and H2. This was motivating to use H3 in a fur- ions, showing low adsorption capacity, which is attrib-
ther study to remove heavy metal ions from water. uted to the low activity of the hydroxyl groups. For that,
the introduction of versatile, functional groups with
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 8 of 15

Fig. 4 EDX analysis of; DAC, DAC/chitosan, and grafted DAC/chitosan

El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 9 of 15

Fig. 5 Effect of time and pH on the swellability of the grafted DAC/

chitosan

high activity, such as nitrile, carboxyl, amine, sulfur, and

amino groups, have been explained to improve the activ-
ity of cellulosic materials to act as ligands for metal ions,
which leads to an increase the adsorption capacity [45].
Furthermore, the arrangement and distribution of the
inserted functional groups in a tighter space as a result
of the hybridization of functionalized cellulose and chi-
tosan, followed by grafting of polyacrylic acid chains,
which was confirmed by several techniques, provides
a suitable environment for selective coordination with
metal ions on a competitive basis in the case in a group
of metal ions are present. Therefore, it was initially essen-
tial to study the adsorption of different elements, such
as ­Pb2+, ­Ni2+, and ­Cu2+, when they are present as binary Fig. 6 Effect of contact time and pH on the adsorption of binary
solution comprising 10 mg/L of ­(Pb2+, ­Ni2+) and ­(Ni2+, ­Cu2+)
mixtures. Thus, the graft copolymer was left in prolonged
on the grafted DAC/chitosan using adsorbent dose of 1 g/L
contact time with binary mixtures of ­(Pb2+, ­Ni2+) and over contact time of 120 min, at pH ≈ 5.6, and room temperature
­(Ni2+, ­Cu2+) until equilibrium was achieved, as displayed
in Fig. 6. Unfortunately, clear discrimination between
these elements was very hard, except at the beginning
of 60 min for the binary mixture ­(Pb2+, ­Ni2+), which On the other hand, the pH of aqueous solutions is one
means that the graft copolymer shows similar affinity to of the most important controlling parameters affecting
such elements under these conditions up to 90 min for the adsorbent efficiency for removing metal ions. The
the mixtures. After that, the adsorption equilibrium was impact of pH on the adsorption of ­(Pb+2, ­Ni+2) and ­(Ni+2,
reached in 150–180 min. ­Cu+2) binary mixtures using the prepared adsorbent was
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 10 of 15

investigated as a function of pH in the range 2.2–5.6.

We could not go farther in this range because OH could
Pb Ni
precipitate these metal ions to form metal (II) hydroxide
above pH 6. The results are depicted for the ion mixtures
in Fig. 6. The extractability of the ions from the solution
increased with the elevation of the pH from 2.2 to 5.6,
which can be attributed to the solubility enhancement of
the metal ions and the degree of ionization of the adsor-
bent during removal. The maximum removal efficiencies
of ­(Pb+2, ­Ni+2) and ­(Cu+2, ­Ni+2) reached (80.6, 79.9%)
and (60.2, 64.4%), respectively. Under strongly acidic
conditions, the adsorbent surface is entirely protonated
with hydronium ions, which strongly oppose metal ions
adsorption on the active sites. However, the separately
of the adsorbent for ­Pb+2 and ­Ni+2 was very weak, espe-
cially at pH values of 2.2 and 5.6. On the contrary, for the
mixture of C ­ u+2, and ­Ni+2, the separately is enhanced at
pH between 3.3 and 4 while diminished at 2.2 or 5.6.

Fig. 7 Pseudo-first-order plot for the adsorption of the binary

Adsorption kinetics solution ­(Pb2+, ­Ni2+) and ­(Cu2+, ­Ni2+) onto the grafted DAC/chitosan
The kinetic investigations of adsorption of the binary (pH ≈ 5.6, concentration of metal ions 10 mg/L, adsorbent dose
mixtures of the elements, as mentioned above, were stud- 1 g/L)
ied to enable prediction of the rate at which these metal
elements can be removed from aqueous solutions and
provide an understanding of the adsorption mechanism. Pseudo‑second‑order
Different known kinetic models were employed for such The pseudo-second-order kinetic is developed to express
a purpose. the adsorption system of divalent metal ions onto an
adsorbent [47]. The following equation can express the
second-order kinetics:
Pseudo‑first‑order 1 t
The rate of metal ions adsorption on an adsorbent is t/qt = +
(k2, ads × qe)2 qe
based on its capacity to accommodate such ions. The
pseudo-first-order model is applied to determine the where ­k2 (g/mg min) is the rate constant of second-order
mass transfer coefficient [46]. The integral form of the adsorption.
pseudo-first-order model can be generally expressed as A linear plot of t/qt versus t is shown in Fig. 8 for the
follows: binary solution ­(Cu2+, ­Ni2+) with a relatively low ­R2. In
k1, ads contrast, the experimental ­qe values disagree with the
log(qe − qt) = logqe − Xt calculated values obtained from the linear plots.
2.303
On the other hand, in the case of the binary solution
where ­qe and q ­t are the amounts of metal ions ­(Pb2+, ­Ni2+), the obtained ­R2 values from the correspond-
adsorbed(mg/g) at equilibrium and at time t (min), ing plots (Fig. 8) were satisfactory high (0.965, 0.919 for
respectively, while k­ 1(1/min) is the rate constant of first- ­Pb2+, ­Ni2+, respectively). However, the experimental q ­e
order adsorption. values did not agree with the calculated values obtained
Plotting of log ­(qe–qt) versus t for the binary ions mix- from the linear plots.
tures of ­(Pb2+, ­Ni2+) and ­(Ni2+, ­Cu2+) are presented in These data reveal the second-order kinetic model could
(Fig. 7). The corresponding ­R2 values are 0.977, 0.966 for be better for describing the adsorption process of (­Cu2+,
­(Pb2+, ­Ni2+) and 0.9, 0.936 for ­(Ni2+, ­Cu2+), respectively, ­Ni2+) on the graft copolymer whereas for the binary mix-
indicating good conformity between the experimen- ture ­(Pb2+, ­Ni2+) the first-order kinetic model prevail.
tal and calculated ­qe values, which reflects the excellent
applicability of this model to describe the adsorption Adsorption isotherms
process of (­Pb2+, ­Ni2+) and (­Ni+2, ­Cu2+) ions onto the Adsorption isotherms present parameters that describe
graft DAC/chitosan. the affinity of an adsorbent towards specific adsorbates
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 11 of 15

900 A linear plot of Langmuir adsorption isotherm ­(Ce/qe

800 Pb Ni
700 y = 2.8648x + 296.74 vs. ­Ce) demonstrates the validity of Langmuir isotherm
t/qt (min.g/meq)

R² = 0.8966
600 y = 1.71220x + 388.81147 to follow the adsorption of metal ions as revealed in
500 R² = 0.81579 Fig. 9. The values of ­qmax and K for ­(Pb2+, ­Ni2+) and
400
300 ­(Cu2+, ­Ni2+) ions were calculated from the slope and
200 the intercept of the linear plots ­Ce/qe versus ­Ce. The
100
0
results are given in Table 1, which showed a good fit
0 50 100 150 200 was achieved for the data with the Langmuir isotherm
Time (min.) model. Further, the Langmuir parameters can also be
2500 employed to deduce the affinity between the different
2000 y = 8.57454x + 606.27329 metal ions and the grafted DAC/chitosan as adsorbent
t/qt (min.g/meq)

R² = 0.96504 using a dimensionless separation factor ­(RL), which can

1500
be defined from the following equation [49]:
1000 y = 1.7099x + 224.85
R² = 0.9195
500
RL = 1/1 + (K Co )
0
0 50 100 150 200
Time (min)
Fig. 8 Pseudo-second-order plot for binary solution of ­(Cu2+, ­Ni2+)
and ­(Pb2+, ­Ni2+) adsorption onto the grafted DAC/chitosan (pH ≈5.6,
concentration of metal ions 10 mg/L, adsorbent dose 1 g/L)
3.6
Pb Ni
3.1

2.6 y = 0.035x + 0.3245

Ce/ Cads (g/L)

such as metal ions. Investigation of the performance of 2.1 R² = 0.9947

a polymeric adsorbent is significant for getting a pre- 1.6

y = 0.0068x + 0.2173
cise equilibrium correlation between the solid and liq- 1.1
R² = 0.9446
uid-phase concentrations of metal ions [48]. Thus, it is 0.6

essential to find the corresponding equilibrium data for 0.1

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
removing of metal ions such as (­Pb2+, ­Ni2+) and (­Cu2+, Ce (mg/L)
­Ni2+) using the developed graft copolymer with different 8
isotherm models. 7 Cu Ni

6 y = 0.0713x + 0.727
R² = 0.9584
Ce/Cads (g/L)

5
Langmuir isotherm 4
y = 0.0255x + 0.2622
The Langmuir isotherm model [49] has been widely 3
R² = 0.9994
used innumerous processes of metal ions removal via 2
1
adsorption. It is based on the assumption that metal
0
ions uptake proceeds on a homogeneous surface via 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
monolayer adsorption without any interaction between Ce (mg/L)

adsorbed metal ions, considering that all adsorption sites Fig. 9 Langmuir model isotherm for binary solution of ­(Pb2+,
have equal activity. In contrast, the adsorption at one ­Ni2+) and ­(Cu2+, ­Ni2+) adsorption onto the grafted DAC/chitosan
after contact for 120 min using adsorbent dose of 1 g/L at pH ≈ 5.6)
site will not affect the adsorption at a neighboring site.
Accordingly, the Langmuir isotherm is best applicable for
monolayer adsorption onto a surface containing a finite
number of identical sites. It can be expressed by the fol- Table 1 The separation factor for the binary solutions of ­(Pb2+,
lowing equation: ­Ni2+) and (­ Cu2+, ­Ni2+) adsorption on the grafted DAC/chitosan
  Co (mg/L) (Pb2+, ­Ni2+) (Cu2+, ­Ni2+)
Ce /qe = 1/ K × qmax + Ce /qmax
­ b2+
RL of P ­ i2+
RL of N ­ i2+
RL of N RL of ­Cu2+
where ­Ce is the concentration at equilibrium (mg/L), ­qe
10 0.0152 0.0156 0.017 0.0159
is the adsorbed amount at equilibrium (mg/g), q ­ max is
30 0.0051 0.00524 0.00569 0.00531
the maximum adsorption capacity corresponding to the
60 0.00243 0.0026 0.00285 0.00265
complete monolayer coverage (mg/g), and K is the Lang-
110 0.00132 0.00143 0.00158 0.0015
muir constant related to the adsorption energy.
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 12 of 15

where K is the Langmuir constant (L/mg) and C ­ o is the indicates an adsorbent’s surface heterogeneity, while it
concentration of metal ions, mg/L. The R ­ L value indicates can be expressed by the following equation:
whether the adsorption is unfavorable (­ RL > 1), ­(RL = 1) or
1
favorable (0 < ­RL < 1), or irreversible (­ RL = 0). logqe = logKf + logCe
Figure 9 shows that the adsorption of (­Pb+2, ­Ni+2) and n
­(Cu+2, ­Ni+2) increased in parallel with a concentration of where ­KF and 1/n are constants ascribed to capacity and
metal ions. In addition, the obtained R ­ L values for these intensity of adsorption process, respectively.
metal ions` adsorption indicate that adsorption is favora- ­ F for (­ Pb2+, ­Ni2+) and (­ Cu2+, ­Ni2+)
The values of n and K
ble even at higher concentrations of metal ions (Table 1). ions were obtained from the slope and the intercept of
linear plots between log ­qe versus log ­Ce (Fig. 10) while
Freundlich isotherm the related correlation coefficients (­R2) are presented in
The Freundlich isotherm theory [50] dictates that the Tables 2. Interestingly, the ­R2 values confirmed that the
ratio of adsorbate amount to a given mass of adsorbent developed grafted DAC/chitosan exhibits good fit with
concerning the adsorbate concentration in a solution is both Langmuir and Freundlich isotherms.
not constant at different concentrations. The magnitude
of adsorption heat decreases with increasing the extent of Selective removal of metal ions by grafted DAC/chitosan
adsorption. The Freundlich isotherm adsorption model The adsorption activity of the prepared adsorbent
(grafted DAC/chitosan) was investigated towards metal
ions existing together at equal initial concentrations.
This was undertaken at different concentrations in the
10–110 mg/L range of each ion while the pH was kept
constant at 5.6, as displayed in Fig. 11.
Generally, it can be observed that the removal of the
grafted DAC/chitosan towards metal ions is increased to
68.1, 23.6% for the combination of ­Pb2+ and ­Ni2+, respec-
tively, and 45.5 and 18.2% for the combination ­Cu2+ and
­Ni2+ when the metal ions concentration is increasing
from 10 to 110 mg/L. This phenomenon is most likely
due to the saturation of the active sites of the adsorbent
with the metal ions at higher concentrations, keeping in
mind that the preference for ­Pb2+/ ­Cu2+ against ­Ni2+ is
predominant for all combinations. Interestingly, a selec-
tive removal and more effective separation of the metal
ions from each other can be achieved at higher concen-
trations. In contrast, this trend appears more evident in
the case of ­Pb2+/ ­Ni2+ than in the other systems. This
behavior is presumably related to a minor extent to the
­ i2+ concerning other ions and, to a sig-
bigger size of N
nificant degree, to the nature of the polymeric material,
Fig. 10 Freundlich isotherm for binary solution of ­(Pb2+, ­Ni2+)
which can be supported by the high removal capacity
and ­(Cu2+, ­Ni2+) adsorption onto the grafted DAC/chitosan
after contact for 120 min using adsorbent dose of 1 g/L at pH ≈ 5.6 of these ions without competitive disturbance from the

Table 2 Summary of isotherm models parameters for ­(Pb2+, ­Ni2+) and (­ Cu2+, ­Ni2+) adsorption onto the grafted DAC/chitosan
Binary mixture Metal Langmuir model Freundlich model
ion
K qmax R2 Kf n R2
L/mg (mg/g)

(Pb2+/ ­Ni2+) Ni2+ 6.3 28.57 0.995 5.98 2.89 0.9888

Pb2+ 6.49 147.06 0.9446 5.13 1.254 0.9729
(Cu2+/ ­Ni2+) Ni2+ 5.76 14.03 0.9584 4.55 4.57 0.959
Cu2+ 6.18 39.22 0.999 4.86 1.95 0.948
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 13 of 15

Table 3 Repetitive cycles for removal of ­Pb2+, ­Ni2+, and ­Cu2+

from their binary mixtures at optimized operating conditions
Mixture → (Pb2+/ ­Ni2+) (Cu2+/ ­Ni2+)
Cycle ↓ Pb+2 Ni+2 Cu2+ Ni2+
Q (mg/g) Q (mg/g) Q (mg/g) Q (mg/g)

1 8.1 7.7 8.3 8.1

2 7.5 7 7.9 7.6
3 7 6.5 7.4 7.4

­ i2+, the retained activity in the second and third

case of N
cycles reached 93.8 and 91.4%, respectively.

Conclusions
Cellulose can be functionalized via oxidation to gain high
content of aldehyde groups on its surface. The aldehyde-
functionalized cellulose can be coupled with chitosan
to yield a chemically active backbone with improved
handling and high surface area, making it a viable back-
bone for grafting copolymerization with acrylic acid.
This has driven the resulting highly versatile structure
to acquire a porous network incorporating pores of vari-
Fig. 11 Effect of initial ions concentration of ­Pb2+, ­Ni2+, and ­Cu2+ ous size distributions. The functionalization with copious
in a binary mixture of ­(Pb2+, ­Ni2+) and ­(Cu2+, ­Ni2+) on the adsorption hydrophilic groups and complicated mesh structure are
into the grafted DAC/chitosan at operating conditions (contact time deemed the driving force for elevated swelling in aqueous
120 min, adsorbent dose1 g/L at pH ≈ 5.6)
media. Such characteristics can qualify this novel mate-
rial to act as an active adsorbent for heavy metal ions on a
competitive basis from their aqueous mixtures. The high
swelling capacity of the adsorbent (872%) was referred to
present ­Ni2+. More interestingly, the removal of N­ i2+ is
as the developed high porosity with various size distribu-
still relatively superior with respect to other comparable
tions as watched by SEM. A selective adsorption trend
materials, even in the presence of other competing ions
for efficient removal of ­Ni2+can be achieved, even though
[51].
other competing ions of smaller size, such as ­Pb2+and
­Cu2+, are present. The extensive crowding of polymeric
Desorption studies
chains with various functional groups distributed over
The ability to desorb metal ions from an adsorbent is an
pores with multiple-size distributions is responsible for
important factor in determining the lifetime of the adsor-
such selectivity. The kinetic study showed the adsorp-
bent. Thus, regenerability of hydrogel was investigated.
tion of P­ b2+, ­Ni2+, and C
­ u2+ in a binary mixture of (­ Pb2+,
The results of the performance of the sorbents for the 2+ 2+ 2+
­Ni ) and ­(Cu , ­Ni ) onto the grafted DAC/chitosan fit
removal of metal ions from binary mixtures are collected
with both Langmuir and Freundlich isotherms. In addi-
in Tables 3, where it can be emphasized that the sorb-
tion, the grafted DAC/chitosan hydrogel exhibited excel-
ent was very active for the removal of the ions during the
lent reusability. This study provided a highly efficient
second and third cycles and maintained 92.6 and 86.4%
bioadsorbent for the removal of heavy metals from an
compared with the original activity of sorbent during the
aqueous solution.
first cycle, respectively, in case of ­Pb2+. In contrast, in the
case of ­Ni2+, the sorbent retained 99.9 and 84.4% for the Acknowledgements
second and third cycles compared with the first one. The authors thank the National Research Centre, Egypt, for the facilities
support.
The sorbent behaved very similarly in the case of the
binary mixture of C ­ u2+ and ­Ni2+, where the activity of the Author contributions
sorbent to remove ­Cu2+ in the second cycle was 95.2% ESAES: proposed the work plan and performed the synthesis and characteriza‑
tion. SD: performed the synthesis and characterization, and writing the manu‑
concerning its activity during the first cycle, declined to script. HAE: proposed the work plan, writing and reviewing the manuscript.
89.2% during the third one. On the other hand, in the HSI: adsorption study and writing the manuscript. NSA; adsorption study
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 14 of 15

and writing the manuscript. SK: conceptualization, validation, reviewing the 13. Ibrahim AG, Saleh AS, Elsharma EM, Metwally E, Siyam T. Chitosan-g-
manuscript, and project administration. All authors have approved the final maleic acid for effective removal of copper and nickel ions from their
version of the manuscript. solutions. Int J Biol Macromol. 2019;121:1287–94.
14. Hilmioglu ND, Tulbentci S. Separation of IPA/water mixtures by
Funding pervaporation: sorption and pervaporation results. Vacuum.
Open access funding provided by The Science, Technology & Innovation 2003;72(1):35–40.
Funding Authority (STDF) in cooperation with The Egyptian Knowledge Bank 15. Tüysüz M, Köse K, Aksüt D, Uzun L, Evci M, Köse DA, Youngblood JP.
(EKB). Removal of atrazine using polymeric cryogels modified with cellulose
nanomaterials. Water Air Soil Pollut. 2022;233(11):472.
Availability of data and materials 16. Köse K, Mavlan M, Nuruddin M, Gómez AMU, Youngblood JP. Modifica‑
All data and materials are available. tion of glycidyl methacrylate based cryogels by cellulose nanocrys‑
tals and determination of dye adsorption performance. Cellulose.
2022;29(3):1623–36.
Declarations 17. Köse K, Mavlan M, Uzun L, Youngblood JP. Cholesterol removal via
cyclodextrin-decoration on cellulose nanocrystal (CNC)-grafted poly
Ethics approval and consent to participate (HEMA-GMA) nanocomposite adsorbent. Cellulose. 2021;28:471–87.
Not applicable. 18. Köse K, Mavlan M, Nuruddin M, Youngblood JP. TEMPO-oxidized cel‑
lulose nanofiber based polymeric adsorbent for use in iron removal.
Consent for publication Cellulose. 2020;27:4623–35.
Not applicable. 19. Dalei G, Das S, Pradhan M. Dialdehyde cellulose as a niche material for
versatile applications: an overview. Cellulose. 2022;29(10):5429–61.
Competing interests 20. Duceac IA, Tanasa F, Coseri S. Selective oxidation of cellulose—a
The authors declare no competing interests. multitask platform with significant environmental impact. Materials.
2022;15(14):5076.
21. Hasanin M, Hashem AH, El-Rashedy AA, Kamel S. Synthesis of novel
Received: 31 January 2023 Accepted: 7 September 2023 heterocyclic compounds based on dialdehyde cellulose: characteriza‑
tion, antimicrobial, antitumor activity, molecular dynamics simulation
and target identification. Cellulose. 2021;28:8355–74.
22. Lavoine N, Desloges I, Dufresne A, Bras J. Microfibrillated cellulose–Its
barrier properties and applications in cellulosic materials: a review.
References Carbohyd Polym. 2012;90(2):735–64.
1. Karlsson HO, Trägårdh G. Pervaporation of dilute organic-waters mixtures. 23. Siró I, Plackett D. Microfibrillated cellulose and new nanocomposite
A literature review on modelling studies and applications to aroma materials: a review. Cellulose. 2010;17:459–94.
compound recovery. J Memb Sci. 1993;76(23):121–46. 24. Chin KM, Sung Ting S, Ong HL, Omar M. Surface functionalized nano‑
2. Nguyen QT, Le Blanc L, Neel J. Preparation of membranes from polyacry‑ cellulose as a veritable inclusionary material in contemporary bioin‑
lonitrile—polyvinylpyrrolidone blends and the study of their behaviour spired applications: a review. J Appl Polym Sci. 2018;135(13):46065.
in the pervaporation of water—organic liquid mixtures. J Membr Sci. 25. Grossman RF, Nwabunma D: Biopolymer nanocomposites: processing,
1985;22(2–3):245–55. properties, and applications: Wiley; 2013.
3. Csavina J, Field J, Félix O, Corral-Avitia AY, Sáez AE, Betterton EA. Effect of 26. Arsad NJ, Ngadi N, Mohamed Razak SF: Preparation of chitosan-grafted
wind speed and relative humidity on atmospheric dust concentrations in nanocellulose via microwave-initiate method. In: Applied Mechanics
semi-arid climates. Sci Total Environ. 2014;487:82–90. and Materials: 2016. Trans Tech Publ: 281–284.
4. Jiraratananon R, Chanachai A, Huang R, Uttapap D. Pervaporation 27. Sadeghi M. Synthesis and swelling behaviors of graftcopolymer based
dehydration of ethanol–water mixtures with chitosan/hydroxyethylcel‑ on chitosan-g-poly (AA-co-HEMA). Int J Chem Eng Appl. 2010;1(4):354.
lulose (CS/HEC) composite membranes: I. Effect of operating conditions. 28. Sudhavani T, Reddy NS, Rao KM, Rao K, Ramkumar J, Reddy A. Devel‑
J Membr Sci. 2002;195(2):143–51. opment of thiourea-formaldehyde crosslinked chitosan membrane
5. Tsai H, Chen H, Chou W, Lee K, Yang M, Lai J. Pervaporation of water/alco‑ networks for separation of Cu (II) and Ni (II) ions. Bull Korean Chem Soc.
hol mixtures through chitosan/cellulose acetate composite hollow-fiber 2013;34(5):1513–20.
membranes. J Appl Polym Sci. 2004;94(4):1562–8. 29. Trang TTC, Nhung NT, Kobayashi T. Fabrication and characterization of
6. Suto S, Ui N. Chemical crosslinking of hydroxypropyl cellulose and chi‑ pulp/chitosan composite membranes crosslinked with 3-Methylglu‑
tosan blends. J Appl Polym Sci. 1996;61(13):2273–8. taric Anhydride for pervaporation of ethanol/water mixture. Engineer‑
7. Sun J, Xu F, Geng Z, Sun X, Sun R. Comparative study of cellulose isolated ing. 2011;3(2):110.
by totally chlorine-free method from wood and cereal straw. J Appl 30. Wang Z, Liu J, Zhang J, Hao S, Duan X, Song H, Zhang J. Novel chemi‑
Polym Sci. 2005;97(1):322–35. cally cross-linked chitosan-cellulose based ionogel with self-healability,
8. Schutter DJ, van Honk J, d’Alfonso AA, Peper JS, Panksepp J. High high ionic conductivity, and high thermo-mechanical stability. Cel‑
frequency repetitive transcranial magnetic over the medial cerebellum lulose. 2020;27:5121–33.
induces a shift in the prefrontal electroencephalography gamma spec‑ 31. Essawy HA, Ghazy MB, Abd El-Hai F, Mohamed MF. Superabsorbent
trum: a pilot study in humans. Neurosci Lett. 2003;336(2):73–6. hydrogels via graft polymerization of acrylic acid from chitosan-cellu‑
9. Kittur A, Kariduraganavar M, Toti U, Ramesh K, Aminabhavi T. Per‑ lose hybrid and their potential in controlled release of soil nutrients. Int
vaporation separation of water–isopropanol mixtures using ZSM-5 J Biol Macromol. 2016;89:144–51.
zeolite incorporated poly (vinyl alcohol) membranes. J Appl Polym Sci. 32. Mohamed MF, Zhou X, Ibrahim HS, Ammar NS, Essawy HA. Grafting
2003;90(9):2441–8. polymerization of acrylic acid onto chitosan-cellulose hybrid and appli‑
10. Seeram N, Lee R, Hardy M, Heber D. Rapid large scale purification of cation of the graft as highly efficient ligand for elimination of water
ellagitannins from pomegranate husk, a by-product of the commercial hardness: validation of high selectivity in presence of interfering ions.
juice industry. Sep Purif Technol. 2005;41(1):49–55. Int J Biol Macromol. 2018;116:530–6.
11. Omer AM, Dey R, Eltaweil AS, Abd El-Monaem EM, Ziora ZM. Insights into 33. Essawy HA, Ghazy MB, El-Hai F, Mohamed MF. Novel chitosan-cellulose
recent advances of chitosan-based adsorbents for sustainable removal of backbone for grafting polymerization of acrylic acid and application in
heavy metals and anions. Arab J Chem. 2022;15(2): 103543. controlled release. J Chem Chem Sci. 2015;5(12):698–712.
12. He Y, Gou S, Zhou L, Tang L, Liu T, Liu L, Duan M. Amidoxime-functional‑ 34. Abou-Yousef H, Dacrory S, Hasanin M, Saber E, Kamel S. Biocompatible
ized polyacrylamide-modified chitosan containing imidazoline groups for hydrogel based on aldehyde-functionalized cellulose and chitosan for
effective removal of Cu2+ and Ni2+. Carbohyd Polym. 2021;252: 117160. potential control drug release. Sustain Chem Pharm. 2021;21: 100419.
El‑Sayed et al. BMC Chemistry (2023) 17:117 Page 15 of 15

35. Abou-Zeid RE, Dacrory S, Ali KA, Kamel S. Novel method of preparation of
tricarboxylic cellulose nanofiber for efficient removal of heavy metal ions
from aqueous solution. Int J Biol Macromol. 2018;119:207–14.
36. Abdelaziz AM, Dacrory S, Hashem AH, Attia MS, Hasanin M, Fouda HM,
Kamel S, ElSaied H. Protective role of zinc oxide nanoparticles based
hydrogel against wilt disease of pepper plant. Biocatal Agric Biotechnol.
2021;35: 102083.
37. Dacrory S, Hashem AH, Kamel S. Antimicrobial and antiviral activities
with molecular docking study of chitosan/carrageenan@ clove oil beads.
Biotechnol J. 2022;17(2):2100298.
38. Eaton A: APHA (American Public Health Association), AWWA (American
Water Works Association), and WEF (Water Environment Federation).
2005. Standard methods for the examination of water and wastewater
21th ed Method.
39. Abd El-Aziz M, Youssef A, Kamal KH, Kelnar I, Kamel S. Preparation and
performance of bionanocomposites based on grafted chitosan, GO
and TiO2-NPs for removal of lead ions and basic-red 46. Carbohydrate
Polymers. 2023;305: 120571.
40. El Nahrawy AM, Ali AI, Mansour A, Abou Hammad AB, Hemdan BA, Kamel
S. Talented Bi0. 5Na0. 25K0. 25TiO3/oxidized cellulose films for optoelec‑
tronic and bioburden of pathogenic microbes. Carbohydrate Polymers.
2022;291: 119656.
41. Abd El-Aziz M, Kamal KH, Ali K, Abdel-Aziz M, Kamel S. Biodegradable
grafting cellulose/clay composites for metal ions removal. Int J Biol Mac‑
romol. 2018;118:2256–64.
42. Abou‐Yousef H, Kamel S: High efficiency antimicrobial cellulose‐based
nanocomposite hydrogels. J Appl Polymer Sci 2015, 132(31).
43. Saeed AA, Abbas MN, Singh B, Abou-Zeid RE, Kamel S. Cellulose
nanocrystals decorated with gold nanoparticles immobilizing GOx
enzyme for non-invasive biosensing of human salivary glucose. Anal
Methods. 2019;11(48):6073–83.
44. Kamel S. Rapid synthesis of antimicrobial paper under microwave irradia‑
tion. Carbohyd Polym. 2012;90(4):1538–42.
45. Rahman ML, Fui CJ, Sarjadi MS, Arshad SE, Musta B, Abdullah MH, Sarkar
SM, O’Reilly EJ. Poly (amidoxime) ligand derived from waste palm fiber for
the removal of heavy metals from electroplating wastewater. Environ Sci
Pollut Res. 2020;27:34541–56.
46. Yao C, Zhu C. A new multi-mechanism adsorption kinetic model and its
relation to mass transfer coefficients. Surfaces Interfaces. 2021;26: 101422.
47. El-Kady AM, Ali AF, Farag MM. Development, characterization, and in vitro
bioactivity studies of sol–gel bioactive glass/poly (l-lactide) nanocom‑
posite scaffolds. Mater Sci Eng, C. 2010;30(1):120–31.
48. Salem NM, Ebraheem KA, Mubarak MS. The effects of spacer groups on
the chelation characteristics of some new mannich polymers containing
8-hydroxyquinoline. React Funct Polym. 2004;59(1):63–9.
49. Rajabi M, Keihankhadiv S, Suhas J, Tyagi I, Karri RR, Chaudhary M, Mubarak
NM, Chaudhary S, Kumar P, Singh P. Comparison and interpretation of iso‑
therm models for the adsorption of dyes, proteins, antibiotics, pesticides
and heavy metal ions on different nanomaterials and non-nano materi‑
als—a comprehensive review. J Nanostruct Chem. 2023;13(1):43–65.
50. Ahmad R, Ansari K. Fabrication of alginate@ silver nanoparticles (Alg@
AgNPs) bionanocomposite for the sequestration of crystal violet dye from
aqueous solution. Int J Biol Macromol. 2022;218:157–67.
51. Shukla S, Pai RS, Shendarkar AD. Adsorption of Ni (II), Zn (II) and Fe (II) on
modified coir fibres. Sep Purif Technol. 2006;47(3):141–7.

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