Chemical Engineering Journal 481 (2024) 148411

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Chemical Engineering Journal

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Bio-based iron oxide nanoparticles forming bi-functional chitosan

composite adsorbent for Cr(VI) decontamination
Aquib Jawed a, Animes K. Golder a, b, Lalit M. Pandey a, c, *
a
Centre for the Environment, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India
b
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India
c
Bio-interface & Environmental Engineering Lab, Department of Biosciences and Bioengineering, Indian Institute of Technology Guwahati, Guwahati, Assam 781039,
India

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

Keywords: Iron oxide nanoparticles (IONPs) synthesized in a bio-based route are viable contenders for the removal of Cr(VI)
Green synthesis process from contaminated water. However, recovery and reuse of these IONPs are challenging and could limit their
Iron oxide nanoparticles practical applicability. Herein, reusable and bi-functional composite chitosan (CS) beads (CS/IONPs) are
Bi-functional composite adsorbent
developed by infusing IONPs in the CS matrix and applied for Cr(VI) adsorption and detoxification from synthetic
Cr(VI) detoxification
Regeneration and reuse
wastewater. CS/IONPs beads were characterized through various analytical techniques: X-ray diffraction, X-ray
photoelectron spectroscopy and Scanning electron microscopy. The loading of IONPs varied from 0.1 to 0.25 (%
w/v) with Fe(III)/Fe(II) in a molar ratio of 2. Mesoporous (11.65 nm) CS/IONPs beads with a size from 6.6 −
4.31 mm were formed with a specific surface area of 63.67 m2/g compared to 25.42 m2/g for CS beads. Cr(VI)
removal of 98.71 % was achieved by CS/IONPs adsorbent within 480 min at the optimal conditions of initial pH
3, CS/IONPs dosage 2.5 g/L, temperature 25 ◦ C, and initial Cr(VI) concentration 150 mg/L. The co-existing
cations didn’t affect Cr(VI) adsorption capacity of CS/IONPs beads, though PO3− 2−
4 and SO4 competed slightly
with Cr(VI) adsorption. Cr(VI) removal process was spontaneous and exothermic and followed the pseudo-first-
order kinetic. CS/IONPs composite beads could adsorb a maximum of 345.53 mg Cr(VI) per g of IONPs as
determined by Langmuir isotherm. The used CS/IONPs beads could be regenerated using NaOH for the initial 4
cycles, but about 15.7 % of active sites were reduced afterwards. Cr(VI) removal involves electrostatic inter­
action, Cr(VI) reduction to Cr(III), Cr(III) adsorption, Cr(III) surface complexation through abundant –NH2 group,
and Cr(III) co-precipitation with Fe(III).

1. Introduction chemicals that pose a significant risk to the general public’s well-being
[4]. World Health Organisation and US Environmental Protection
The availability of clean, consumable water has been a priority and a Agency have recommended a value of 50 µg/L of maximum contaminant
formidable challenge for humankind. The presence of toxic heavy metals level for Cr(VI) in drinking water [5]. Therefore, to achieve this strict
in drinking water could cause significant health problems and irre­ potable water quality standard, an effective and sustainable technology
versible environmental damage. The elimination of chromium (Cr) from for Cr(VI) decontamination is urgently needed. Especially for indepen­
filthy water streams has been a potential concern to protect people’s dent systems for drinking water supplies that are directly accessible to
health [1]. Cr typically exists in an aqueous system in two stable rural and urban consumers must be upgraded, considering the cost-
oxidation states, namely, Cr(III) and Cr(VI). Cr(VI) is a known carcin­ effectiveness of the purification system and its operation.
ogen that emanates from a variety of industrial effluents such as elec­ Various strategies have been employed to remove Cr(VI) from
troplating, manufacturing of chromate, leather processing, alloy polluted water, including membrane filtration, chemical precipitation,
manufacturing, and textile [2] with concentration varying between a electrocoagulation, and adsorption [6–8]. Adsorption is a promising
wide range (0.5–270,000 mg/L) [3]. method to remove Cr(VI) owed to its easiness, cost-effectiveness, and
Further, Cr(VI) has been categorized as one of the 20 most dangerous affordability, making it a preferred choice among various techniques

* Corresponding author at: Centre for the Environment, Indian Institute of Technology Guwahati, Guwahati, Assam 781039, India.
E-mail address: [email protected] (L.M. Pandey).

https://doi.org/10.1016/j.cej.2023.148411
Received 19 October 2023; Received in revised form 21 December 2023; Accepted 27 December 2023
Available online 30 December 2023
1385-8947/© 2023 Elsevier B.V. All rights reserved.
A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

[9–11]. However, the adsorption technology’s efficacy hinges on the make the whole synthesis process environment-friendly [19,20]. How­
sorbent material’s quality. Nowadays, researchers are interested in ever, to be best of our understanding, there have been no prior in­
using nanomaterial-based adsorbents because of their high surface area vestigations performed on the adsorption of Cr(VI) onto CS/IONPs
and tuneable active sites to remove the target pollutants [7,12]. Iron beads, containing IONPs synthesized using leaf extract of Camellia
oxide nanoparticles (IONPs) were considered promising sorbents for sinensis var. Assamica. The specific novelty of the present research in­
removing anionic Cr(VI) ions from an aqueous solution because IONPs cludes the assessment of the synthesized CS/IONPs beads to decon­
are merited with the important characteristics of an effective nano- taminate harmful contaminant Cr(VI) from an aqueous solution along
adsorbent [12]. with its productive regeneration. The influence of various environ­
Nowadays, green synthesized IONPs using plant extracts have gained mental conditions, namely, pH, temperature, CS/IONPs dosage, initial
popularity due to their ability to eliminate the need for hazardous Cr(VI) concentrations, and contact time were studied and optimized.
reducing agents, which ultimately cause secondary pollution [13]. In Furthermore, a comprehensive analysis was conducted to ascertain the
previous work, we synthesized IONPs using Camellia sinensis var. assa­ adsorption efficacy of the CS/IONPs adsorbent concerning the elimina­
mica extract and applied them to remove Cr(VI) from water. With a tion of Cr(VI). The isotherms, kinetics, and thermodynamics in­
maximum adsorption capacity (Qm) of 1272 mg/g, the synthesized vestigations were thoroughly performed. Moreover, several analytical
IONPs are an effective adsorbent for the removal of Cr(VI) [9]. However, methods were used to characterize the synthesized CS/IONPs adsorbent
due to their nano-scale dimensions and low magnetization, the synthe­ and to understand Cr(VI) adsorption behaviour. Finally, the regenera­
sized IONPs pose a challenge for their separation from treated water, tion studies of used CS/IONPs adsorbent were performed and tested for
impeding their recycling applications. One potential approach to Cr(VI) removal to evaluate their practical applicability.
address this limitation involves the impregnation of synthesized IONPs
into a polymer matrix and, further, cross-linked to form the structure of 2. Materials and methods
the beads to make the IONPs insoluble in solution [4,6,14]. The control
pore size in cross-linked polymer provides a suitable space for the 2.1. Materials
impregnating IONPs and allows the formation of a coarse adsorbent
from the cross-linked reactions. In addition, selecting a suitable polymer Chitosan (cat. no: GRM9358; degree of deacetylation: ≥ 75 %),
matrix with particular functional groups can improve the removal effi­ acetic acid glacial (AA) (cat. no: AS001), 1,5-diphenylcarbazide (DPC)
cacy of the synthesized IONPs by creating a synergistic effect. A (cat. no: GRM519), magnesium chloride (cat. no: GRM3922), sodium
commonly available amino polysaccharide, Chitosan (CS), composed of chloride (cat. no: GRM853), sodium phosphate monobasic (cat. no:
amine (NH2) and hydroxyl (OH) groups for heavy metal ions scavenger, GRM3964), calcium chloride (cat. no: GRM534), sodium nitrate (cat. no:
has been widely applied in the treatment of Cr-polluted water [15]. PCT0014) and magnesium sulphate heptahydrate (cat. no: GRM684)
Various reported literature adopted the in-situ and ex-situ chemically were purchased from Himedia, India. Sodium tripolyphosphate (cat. no:
synthesized IONPs-impregnated CS sorbent for Cr(VI) removal [4,16]. 85124) was purchased from Sisco research laboratories Pvt. Ltd. Cr
Recently, Li et al. developed in-situ CS magnetic beads and applied standard solution (1000 mg/L, cat. no: 02733) supplied and prepared
them to treat a 50 mg/L synthetic metal solution of Cr(VI). The syn­ from Ammonium dichromate by Sigma Aldrich, India, was diluted to
thesized beads were determined to remove 99 % of Cr(VI) in 1200 min at lower Cr(VI) concentrations with deionized water to make working so­
a pH of 5. The Qm value for CS magnetic beads was 293.46 mg/g [3]. In lutions for batch adsorption studies. The experimental studies utilized
another study, 99.25 % of Cr(VI) was removed by in-situ synthesized double distilled water that was obtained from a Millipore system (Mili-
composite adsorbent composed of CS/coconut shell activated carbon Q) with a resistivity of 18 MΩ.
modified with iron from 25 mg/L synthetic metallic solution at pH 3
within 2880 min. The synthesized beads exhibited a reported Qm value 2.2. Synthesis of CS/IONPs adsorbent
of 64.5 mg/g [17]. A separate study formed chemically synthesized
IONPs in situ-impregnated CS beads for Cr(VI) removal from 20 mg/L In our earlier work, we used an aqueous extract of Camellia sinensis
aqueous solution. The synthesized beads were found to remove 75 % of var. assamica to synthesize IONPs [9]. The synthesized IONPs exhibited
Cr(VI) at pH 5 within 600 min. The Qm value for the formed beads was a spherical shape, with an average diameter of 21.33 ± 3 nm and
69.8 mg/g [1]. composed of both Fe(III) and Fe(II) at a molar ratio of 2. These IONPS
Further, chemically synthesized Fe0 NPs (nZVI) were added ex-situ in were utilized in the present work to form CS/IONPs beads. For the
the CS matrix to form CS-nZVI beads to remove Cr(VI) from the aqueous synthesis of beads, first, 2 % (w/v) CS was dissolved in 1 % (v/v) AA, and
solution. The synthesized CS-nZVI adsorbent attained a removal of 82 % then 0.25 % (w/v) IONPs were added to the mixture while it was stirred
Cr(VI) from 20 mg/L solution at pH 6.4 in a time duration of 30 min continuously (200 rpm) at room temperature. The resulting mixture was
[18]. However, the entrapment of green synthesized IONPs into the CS frequently swirled for 24 h. Subsequently, the obtained solution was
matrix has not been extensively investigated for Cr(VI) removal. This dropped into a solution of STPP (1 % (w/v)) through a syringe to pro­
urges a demand for environment-friendly composite sorbent of CS for Cr duce spherical CS/IONPs beads (Scheme 1), which were aged for 12 h in
(VI) removal. The ex-situ infusion of green synthesized IONPs in the CS the same solution for hardening. The hardened CS/IONPs beads were
matrix and, thus, forming beads for Cr(VI) removal is still a novel topic rinsed multiple times with double distilled water unless the pH was
for environmental research. The encapsulation of green synthesized neutralized. The same procedure was followed to synthesize bare CS
IONPs onto CS matrix creates a composite material with a composition beads without including IONPs. For further characterization, the syn­
combining organic and inorganic components. Such formed composite thesized CS and CS/IONPs beads were freeze-dried. Cr(VI) removal ex­
materials integrate the features of IONPs (adsorption and reduction) periments were performed through wet beads (CS/IONPs and CS) dosed
with the attributes of CS (complexation and ion-exchange). Therefore, in numbers according to the evaluated dry weight of each synthesized
the formed cross-linked combination of IONPs and CS composite beads.
adsorbent (CS/IONPs beads) is expected to effectively couple the ben­
efits of both materials, resulting in a highly effective composite adsor­ 2.3. Characterization of synthesized beads
bent for Cr(VI) removal.
Accordingly, in the present work, CS/IONPs beads were prepared Fourier transform infrared (FT-IR) spectrometer (PerkinElmer,
through the ex-situ infusion of green synthesized IONPs [9] in the CS Model: Spectrum two, USA) recorded the pertinent functional groups on
matrix. The cross-linking of the CS/IONPs mixture to form spherical CS/IONPs beads within the wavenumber from 4000 to 400 cm− 1. The
beads was performed in sodium tripolyphosphate (STPP) solution to synthesized beads were analyzed using a high-resolution X-ray

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Scheme 1. Adopted protocol of CS and CS/IONPs beads synthesis.

diffractometer (XRD) (Rigaku Technologies, Model: Smartlab, Japan) L), and adsorption kinetics (30–480 min) studies. pH of the solutions
system. The elemental composition of the formed beads was evaluated was adjusted with HCl and NaOH solutions. The equilibrium adsorption
using an X-ray photoelectron spectroscopy (XPS) instrument (Ulvac, capacity (qe, mg/g) and Cr(VI) removal % were calculated as per the
Model: PHI 5000 VersaProbe III, Japan), with Al k (1486.6 eV) as the following relations (Eqs. (1) and (2)).
excitation source. The morphological changes of the synthesized CS
(Co − Ce ) × V
beads after IONPs infusion were examined using Field emission scanning qe = (1)
M
electron microscopy (FESEM) (Zeiss, Model: Sigma, Germany). Energy
dispersive spectroscopy (EDS) (Zeiss, Model: Sigma, Germany) was (Co − Ce )
engaged with synthesized beads for elemental analysis. The particle size Cr(VI) removal % = × 100 (2)
Co
analyzer (Anton Paar, Model: LitesizerTM 500, Austria) was used to
measure the surface charge in mV of the formed beads at various pH Herein, C0 (mg/L) and Ce (mg/L) represent the initial Cr(VI) con­
values (3, 4, 6, 8, 10). CS and CS/IONPs beads thermal stability was centration and the residual Cr(VI) concentration in the aqueous phase
inspected using Differential scanning calorimetry (Netzsch, Model: after reaching adsorption equilibrium. At the same time, V (L) is the
STA449F3A00, Germany) with a Thermo Gravimetric analysis (TGA) volume of the solution, and M (g) is the amount of CS/IONPs beads
System. The surface area of both the synthesized beads was determined added to the solution.
using the Brunauer-Emmette-Teller (BET) instrument (Qunatchrome,
Model: Autosorb-IQ MP, Austria). The mechanical strength of CS and
2.5. Reusability studies of synthesized CS/IONPs beads
CS/IONPs beads in various pH (3, 6, 10) of double distilled water was
analyzed in an Electro-Mechanical Universal Testing Machine (Zwick­
Conducting reusability studies is crucial for determining the prac­
Roell, Model: Z005TNProline, Germany). It was expressed in terms of
tical applicability of an adsorbent. The Cr(VI) desorption experiments
the force (N) value used for the breakdown of a bead under uniaxial
were carried out in accordance with the previously described approach,
compression.
with minor alterations [4,21]. The Cr(VI) loaded CS/IONPs beads were
agitated in a 30 mL glass contactor with 10 mL of 1 M NaOH at 180 rpm
2.4. Removal of Cr(VI) using synthesized CS/IONPs beads in batch and 25 ◦ C for a duration of 4 h. As stated earlier, the concentration of Cr
adsorption (VI) in the post-desorbed supernatant was determined. The desorbed
CS/IONPs beads were then washed in deionized water and allowed to
The experimental procedure involves conducting batch experiments dry. Following the washing procedure, the CS/IONPs beads were sub­
in 30 mL glass bottles at a starting pH of 3.0 and temperature of 25 ◦ C sequently revived into a fresh 150 mg/L Cr(VI) solution for the purpose
unless stated otherwise. CS/IONPs beads (0.25 % w/v) were stirred in of conducting further adsorption study, as outlined in Section 2.4. A
150 mg/L Cr(VI) initial concentration for 8 h in a shaker incubator total of four sequential desorption/adsorption cycles were performed to
(Scigenics, Model: Orbitek-LE, India) at 180 rpm. Following the incu­ investigate the CS/IONPs reusability for Cr(VI) removal.
bation period, the samples underwent centrifugation, resulting in the
supernatant extraction. Further, to evaluate dissolved Cr(VI) concen­ 3. Results and discussion
tration, the recovered supernatant was diluted with DPC reagent and
measured spectrophotometrically at 543 nm [9]. Using Atomic emission 3.1. Characterization of synthesized beads
spectroscopy (Agilent, Model: MP-AES − 4210, USA), the concentrations
of total chromium (Cr(tot)) and Fe were measured in the solution. Cr(III) The synthesized beads of CS and CS/IONPs as depicted in scheme 1
concentration in the aqueous phase was calculated from the difference were spherical with diameters calculated as 5.2 ± 0.38 and 5.1 ± 0.74
between Cr(tot) and Cr(VI) concentrations. mm, respectively. The physical appearance of CS/IONPs was black due
A series of batch adsorption studies were carried out to assess the to the infusion of IONPs (Scheme 1), whereas the CS beads looked white
adsorption efficacy of synthesized CS/IONPs beads. These experiments (Scheme 1). The preparation procedure of CS beads involved using CS
involved the assessment of the effect of pH (3–10), temperature powder containing functional groups, including hydroxyl (–OH) and
(25–45 ◦ C), CS/IONPs beads doses (0.5–3 g/L), co-existing ions (Na+, amine (–NH2) and carbon chains. As a result, the CS beads include C, N,
Ca2+, Mg2+, PO3− 2−
4 , SO4 , NO3 , Cl ), adsorption isotherms (25–900 mg/
− −
and O (Fig. 1(a) and S1(a)). Further, after IONPs infusion in CS, the

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Fig. 1. EDS mapping of (a) CS beads, (b) Fresh CS/IONPs beads, and (c) Used CS/IONPs beads after Cr(VI) adsorption. (O – Oxygen, C – Carbon, N – Nitrogen, Fe –
Iron, Cr – Chromium).

gelated Fe in the CS matrix appeared in the EDS spectrum (Figure S1(b)) respectively, were observed from FESEM micrographs.
and image mapping (Fig. 1(b)). Moreover, upon the reaction of Cr(VI) Fig. 2a displays the XRD patterns of the original CS powder, CS and
with CS/IONPs beads, the mapping (Fig. 1(c)) and EDS spectrum CS/IONPs beads. The CS powder exhibited distinct peaks at 9.7◦ and
(Figure S2) displayed the presence of Cr peaks and surface coverage, 19.5◦ on the 2θ scale, which is attributed to crystals forms I and forms II
revealing Cr adsorption over the formed beads. The lower magnification in CS structure and revealed the existence of CS hydrophilic groups
view of CS (Figure S3(a)) and CS/IONPs (Figure S3(b)) beads exhibited a [21,22]. However, two more broad humps at 30.12◦ and 41◦ also
resemblance and provided a visual representation of the desiccated appeared in CS powder, representing an amorphous carbon structure.
circular surface of the produced beads. The FESEM images of the formed After the formation of CS beads, crystal forms 1 peak disappeared, and
bead’s outer, inner, and cross-section surfaces were also captured to forms II shifted to 19◦ . The broad hump in CS powder at 30.12◦ formed a
reveal the morphological changes between CS (Figures S3(c), S3(e), and distinct peak at 30.3◦ in CS beads, and another hump moved to 40.3◦ .
S3(g)) and CS/IONPs (Figures S3(d), S3(f), and S3(h)) beads. The CS The CS/IONPs beads showed a similar trend as CS beads, with a broad
beads exhibited a smooth outer surface (Figure S3(c)), whereas the CS/ hump at 30.19◦ and narrow humps at 18.74◦ and 40.95◦ , respectively.
IONPs (Figure S3 (d)) variant displayed a rough surface with minor The disappearance and shift of crystal forms I and forms II peaks,
cracks. The inner surface of CS beads (Figure S3(e)) showed a pattern of respectively in CS/IONPs beads might be due to the chelation of Fe3+
cross-linked CS aggregates. However, following the infusion of IONPs with the CS hydrophilic group (–NH2) [4].
(Figure S3(f)), the inner portion displayed gelated and uniformly The N2 adsorption–desorption isotherm study was conducted to
distributed IONPs in the CS matrix. This distribution in the CS matrix determine the BET area of synthesized CS and CS/IONPs beads at 77 K
was infused with various Fe (Fe2+ and Fe3+) species in IONPs. The cross- by plotting the adsorbed quantity (cm3/g) against relative pressure (P/
section micrographs revealed heterogeneous and undulated surfaces for Po) as shown in Fig. 2b. The plotted N2 adsorption–desorption isotherms
CS (Figure S3(g)) and CS/IONPs (Figure S3(h)) beads, respectively. of both CS and CS/IONPs beads exhibited a Type IV isotherm pattern
Following the adsorption of Cr(VI), circular and rough surfaces of CS and an H4 hysteresis loop [23,24]. The specific BET surface area (SBET)
(Figures S4(a) and S4(b)) and CS/IONPs beads (Figures S4(c) and S4(d)), of CS and CS/IONPs beads were found to be 25.42 and 63.67 m2/g,

Fig. 2. (a) XRD spectra of CS powder, CS beads, and CS CS/IONPs beads and (b) Nitrogen adsorption/desorption isotherms of synthesized CS and CS CS/
IONPs beads.

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

respectively. This increase in SBET of CS/IONPs beads confirmed the water treatment at normal temperature.
successful inclusion of IONPs in CS matrix with enhanced porosity. The The mechanical strength of synthesized CS and CS/IONPs beads in
average pore diameter of CS beads was determined to be 6.62 nm, while various pH (3, 6, 10) solutions was expressed in terms of compressive
for CS/IONPs beads, it was found to be 11.65 nm. The total pore volume force (N) for the breakdown of a bead as shown in Figure S7. When
of CS was determined to be 0.04 cm3/g, whereas for CS/IONPs beads it compared to bare CS beads, the CS/IONPs could withstand 54 % more
was estimated as 0.18 cm3/g. This indicates that the inclusion of IONPs compressive force at all pH conditions, for its breakdown (Figure S7).
in CS matrix may improve the adsorptive properties by enabling easy This revealed the enhancement of mechanical strength in the CS beads
access for Cr(VI) ions within the pores. Moreover, after Cr(VI) adsorp­ through the inclusion of nanomaterials, which is also supported by
tion (Figure S5), the SBET, pore diameter, and pore volume of the used previous studies [27,28].
CS/IONPs beads were reduced to 8 m2/g, 4.92 nm, and 0.045 cm3/g,
respectively as compared to pre-adsorbed beads. The decrement in the 3.2. Removal of Cr(VI) through synthesized CS/IONPs beads
surface area of used CS/IONPs beads reveals the occupancy of Cr(VI)
species inside the mesopores of CS/IONPs beads [25]. These findings 3.2.1. Effect of pH and temperature
illustrate that the adsorption of Cr(VI) occurs both on the surface of the Cr(VI) ions exist in various forms in an aqueous solution, including
synthesized CS/IONPs beads and within their mesopores [26]. chromate (CrO2− 4 ), hydrogen chromate (HCrO4 ), and dichromate
−
2−
The thermal stability of the CS and CS/IONPs beads was analyzed (Cr2O7 ), depending upon the solution pH. At a pH range of 2–6, the
using TGA (Figure S6). According to TGA curves, the CS and CS/IONPs predemoninat Cr(VI) species are HCrO−4 and Cr2O2− 2−
7 . While CrO4 be­
beads experienced a weight loss of 16 % at 200 ◦ C, followed by a weight comes the dominating species at pH > 6 [9]. The initial pH was adjusted
loss of 50 and 51 % at 400 ◦ C, respectively. This observed % weight loss between 3 and 10 for Cr(VI) solution for the current adsorption studies.
was caused due to the evaporation of physically adsorbed water mole­ The amount of Cr(VI) adsorbed to CS/IONPs beads depends on the pH.
cules and the decomposition of CS [21]. Upon reaching the termination Cr(VI) removal was maximum (98.71 %) at an initial pH 3 (Fig. 3a). The
temperature of the TGA experiment (800 ◦ C), the final % weight losses Cr(tot) concentration at the same pH in the aqueous phase was also
were 68 and 64 % for CS and CS/IONPs beads, respectively. The weight lowered by 76 % (Fig. 7b) demonstrating the reduction of Cr(VI) species.
reduction was ascribed to the complete degradation of the CS backbone On the other hand, the bare CS beads showed only 34 % removal
under high-temperature conditions and dihydroxylation of Fe oxides (Figure S8) at the similar pH. This postulates that IONPs infused in the
[1]. The TGA curves were also compared to evaluate the difference CS matrix were key candidates responsible for the adsorption and
between the CS and CS/IONPs beads. The analysis indicated no apparent reduction (Eqs. (7) and (8) of Cr(VI) species in the aqueous solution. This
difference between the two types of beads (CS and CS/IONPs) until the assertion was also supported by our earlier finding [9]. Moreover, the
temperature reached 200 ◦ C. It was observed that the initial decompo­ zeta potential magnitude was more positive in the case of CS/IONPs
sition rate of the CS beads was higher as compared to CS/IONPs. After (52.77 mV) than CS (41.63 mV) beads at pH 3 (Figure S9). Further, the
that, at 800 ◦ C, CS beads (68 %) had more mass loss than CS/IONPs –NH2 and –OH functional groups on CS/IONPs beads were also pro­
beads (64 %). This demonstrates that the addition of IONPs reduced the tonated in acidic solutions (pH < 4) [29]. This led to enhanced elec­
amount of weight loss of CS at elevated temperatures. This may occur trostatic interactions compared to CS beads between protonated CS/
due to the bonds between IONPs and chains of CS molecules, which IONPs beads functional groups and Cr(VI) species in acidic conditions
increases the decomposition temperature [21]. Consequently, CS/IONPs (pH 3) (Eqs. (3)–(6).
beads can be considered stable up to 200 ◦ C and suitably applied for
R − NH2 + H+ →R − NH+
3 (3)

Fig. 3. Effect of (a) pH, (b) temperature, (c) dosage, and (d) initial Cr(VI) concentration on Cr(VI) removal through synthesized CS/IONPs beads.

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

existing ions. In this regard, several cations (Na+, Ca2+, Mg2+) and an­
R − NH+ − + −
3 + HCrO4 →R − NH3 ⋯. HCrO4 (4)
ions (PO3− 2−
4 , SO4 , NO3 , Cl ) were individually introduced into the
− −

R − OH + H+ →R − OH+ (5) aqueous Cr(VI) solution at a concentration of 1 and 10 mM, respectively

2
(Fig. 4). The ionic strength (I) of co-existing ions was evaluated as I =
R − OH+ − + −
2 + HCrO4 →R − OH2 ⋯. HCrO4 (6) ∑ 2
[32]. Ci and z donated the concentration of co-existing ions (mol/
Ci z
2

HCrO−4 + 7H+ + 3Fe2+ → 3Fe3+ + Cr3+ + 4H2 O (7) L) and charge, respectively. The I values follow the trend as Ca2+ > Mg2+
> Na+ for cations while PO3− 2−
4 > SO4 > NO3 > Cl in the case of anions.
− −

Cr2 O2−7 + 14H+ + 6Fe2+ → 6Fe3+ + 2Cr3+ + 7H2 O (8) The removal efficacy of Cr(VI) was not significantly altered by the in­
clusion of co-existing cations due to electrostatic repulsion between the
Therefore, IONPs reduction affinity and electrostatic interactions of positively charged CS/IONPs adsorbent and cations at lower pH. The
protonated functional groups (–NH2 and –OH) in CS/IONPs beads at pH lowest % Cr(VI) removal was observed in the case of a higher concen­
3 were responsible for maximum Cr(VI) removal. Further, increased pH tration of Ca2+ ions because of the high I value compared to other cat­
decreased the Cr(VI) removal % from 98.71 to 7. This was due to ions. Due to the lower affinity and I value of NO−3 and Cl− as compared to
decrement in surface charge (5.83 mV, pH 10) (Figure S9) and depro­ other co-existing anions (PO3− 2−
4 and SO4 ), they were found to have less
tonation of the positively charged (–NH2, and –OH) groups over CS/ influence on the removal efficiency of Cr(VI) [2]. The competitive ef­
IONPs beads occurred at high pH due to low H+ ions concentration. This fects of PO3− 2−
4 and SO4 for Cr(VI) elimination were significant. The
causes an electrostatic repulsion between the negatively charged Cr strength of these effects was increased with an increase in the I value of
species and the synthesized CS/IONPs beads. anions. This was due to the identical tetrahedral structure of PO3− 2− ,
4 , SO4
Fig. 3b depicts how temperature influences Cr(VI) removal. Low and Cr(VI) species (HCrO−4 ) [4]. Consequently, PO3− 4 and SO2−
4
temperature showed a better Cr(VI) removal from the aqueous solution. competed with Cr species to access the adsorption sites over CS/IONPs
Specifically, the removal was increased from 47 to 98.71 % as the beads. The IONPs composed of Fe3+ species of Fe and PO3− 4 ions tend to
temperature dropped from 45 to 25 ◦ C. The observed phenomenon can form complexes with Fe3+ species at low pH values, reducing the effi­
be ascribed to the weaker interactions of solute (CS/IONPs beads) – cacy of Cr(VI) removal [9]. The observed results were consistent with
solvent (Cr(VI solution)) at elevated temperatures [9]. Moreover, the previous research on the effect of co-existing ions on Cr(VI) removal
active sites of CS/IONPs beads exhibited stronger chelation with Cr using similar adsorbents [17].
species at reduced temperatures and formed a stable structure [30].
3.2.5. Thermodynamics study
3.2.2. Influence of CS/IONPs beads dosage and contact time The thermodynamic variables for Cr(VI) adsorption through CS/
Fig. 3c illustrates the relationship between the dosage of CS/IONPs in IONPs beads were determined at various temperatures (298, 303, 308,
g/L and the percentage of Cr(VI) removal and qe in mg/g. Cr(VI) 313, and 318 K). The enlisted Eqs. (9)–(11) were utilized to calculate the
removal % was higher with increased CS/IONPs beads doses and ach­ three thermodynamic parameters, namely, Gibbs free energy (ΔG),
ieved a plateau at 3 g/L dosage. This trend started from 31 % to 99 % at enthalpy (ΔH), and entropy (ΔS) change of Cr(VI) removal [33–35].
0.5 and 3 g/L CS/IONPs beads dosages, respectively. However, at 2.5 g/
(9)
◦
L dosage, the Cr(VI) removal (Fig. 3c) reached the plateau. As active ΔG = − RTlnKC
adsorption sites increased, Cr(VI) removal efficiency increased when
(10)
◦ ◦ ◦
more CS/IONPs beads were dosed into the Cr(VI) solution. The earlier ΔG = ΔH − TΔS
finding also supports the correlation between escalated adsorbent (CS/ ◦ ◦
IONPs) dosage and enhanced Cr(VI) removal [19]. However, due to lnKC =
ΔS
−
ΔH
(11)
unoccupied adsorption sites, qe was decreased from 92 to 49 mg/g at 0.5 R RT
and 3 g/L dosages of CS/IONPs beads, respectively. As illustrated in Here, R represents the gas constant (8.314 J mol− 1. K− 1), the dis­
Fig. 5a, the removal of Cr(VI) exhibited a significant increase during the tribution coefficient is depicted through the symbol Kc (qe/C0) is
initial stage, up to 300 min. The observed phenomenon could be dimensionless, and the variable T refers to the adsorption temperature
attributed to the concentration declivity of Cr(VI) and a surplus of un­ expressed in Kelvin.
occupied adhesion spots over CS/IONPs beads [2]. The prolonged con­
tact time exhausted the Cr(VI) adsorption sites, which further delayed Cr
(VI) adsorption on CS/IONPs beads. Meanwhile, the adsorption equi­
librium was achieved within 480 min.

3.2.3. Effect of initial Cr(VI) concentration

A range of initial concentrations was tested to determine optimal
conditions for removing Cr(VI), ranging from 25 to 900 mg/L (Fig. 3d).
Moreover, despite the increase in qe value, the removal % was reduced
as the initial Cr(VI) concentration climbed. This reduction in Cr(VI)
removal % was due to the inverse relation between Cr(VI) removal %
and Co as depicted in Eqs.2 (Section 2.4). On the other hand, qe values
were found to be increased with a rise in Cr(VI) concentrations. This
observed phenomenon was ascribed to the saturation in adsorption spots
of CS/IONPs beads at elevated Cr(VI) concentrations, which were left
vacant at lower concentrations [31]. As a result, 150 mg/L was estab­
lished as an optimal concentration of Cr(VI) for further kinetics tests,
attaining more than 95 % Cr(VI) elimination.

3.2.4. Effect of co-existing ions

The efficacy of the synthesized adsorbent (CS/IONPs beads) in
removing Cr(VI) from contaminated water may be hindered by co- Fig. 4. Effect of co-existing ions on Cr(VI) removal %.

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Fig. 5. Non-linearized fitting of adsorption (a) Kinetics and (b) Isotherms models.

The various thermodynamic parameters as calculated from the

Table 1
linearized fitting of Figure S10. The slope and intercept values of
Parameters for PFO, PSO, Elovich, and IPD kinetic models for the removal of
Figure S10 were employed to quantify the magnitude of ΔH and ΔS,
150 mg/L Cr(VI) using CS/IONPs beads.
respectively. Afterwards, the computed ΔH and ΔS values were equated
in Eqs.10 to evaluate the magnitude of ΔG. The spontaneous occurrence Kinetic Non-Linear Parameters Value RMSE
model expression
of Cr(VI) adsorption through CS/IONPs beads was indicated through
negative magnitudes of ΔG at different temperatures. As the tempera­ PFO qt = qe (1− e− K1 t
) qe (mg g− 1) 58.67
K1 (min− 1) × 10− 3 9
ture increased, the negative magnitude of ΔG values dropped (14.8 to
R2 0.99
13.8 KJ mol− 1), indicating that low temperatures favoured Cr(VI) PSO K2 q2e t qe (mg g− 1) 73.40
adsorption using prepared CS/IONPs beads, as described in section qt =
1 + K2 q2e t K2 (g mg min− 1) × 1.2
3.2.1. Cr(VI) adsorption was facilitated mainly by electrostatic interac­ 10− 4
tion (physisorption), as indicated by values of ΔG < 20 KJ mol− 1 [29]. R2 0.99
Elovich 1 α (mg g min− 1) 0.972
The negative value of ΔH (-29.35 KJ mol− 1) advocated that Cr(VI) qt =
β
Ln(αβt)
β (g mg− 1) 0.052
removal through CS/IONPs beads was an exothermic process. The R2 0.98
magnitude of ΔS was estimated to be − 48.55 J mol− 1 K− 1. This indi­ IPD qt = Ki t0.5 + C Initial 300 min
cated a decrease in randomness at the CS/IONPs beads/liquid interface Kinitial (mg g− 1 min -0.5) 3.22
C (mg g− 1) 0.69
upon Cr(VI) adsorption onto the beads [1].
R2 0.97
After 300 min
3.2.6. Adsorption kinetics Kintra (mg g− 1 min -0.5) 0.425
It is important to look into the kinetics of Cr(VI) adsorption through C (mg g− 1) 49.46
CS/IONPs beads to design an adsorption system properly. The kinetics of R2 0.96

CS/IONPs beads for Cr(VI) adsorption are illustrated in Fig. 5a. Cr(VI)
adsorption was much faster in the first 300 min (Fig. 5a, symbols show fitted results (Figure S11) indicate that Cr(VI) adsorption onto CS/IONPs
experimental data points) and attained 90 % removal owing to abundant beads occurred in stages. Initially, a fast adsorption process happened on
empty sites on CS/IONPs beads. The adsorption rate decelerated and the surface of CS/IONPs beads, which was then succeeded by diffusion
reached a plateau at 480 min due to reduced active sites. through the pores of the beads (up to 300 min). As the active sites and
To gain additional insight into the adsorption process, four pores were saturated by that time (300 min), the adsorption process then
frequently employed kinetic models were utilized to interpret the ki­ moved to the interior pores of beads, i.e., IPD, which continued up to
netics data, namely, pseudo-first-order (PFO), pseudo-second-order 480 min. The values of rate constants for IPD, specifically Kinitial (<300
(PSO), Elovich, and intra-particle diffusion (IPD) models [36]. The min) and Kintra (>300 min), were calculated as 3.22 mg g− 1 min0.5 (R2 =
graph in Fig. 5a displays the qt (mg/g) values obtained from the fitted 0.97) and 0.425 mg g− 1 min0.5 (R2 = 0.96), respectively. The compar­
kinetic models plotted against time (min), represented by the fitted atively higher value of Kinitial to Kintra indicated a more rapid adsorption
lines. Table 1 shows the model parameters of the fitted models to the rate during the initial phases of Cr(VI).
experimental data and their corresponding root mean square error
(RMSE) and correlation coefficient (R2) values. 3.2.7. Adsorption isotherm
As depicted in Table 1, the PSO model exhibited the lowest RMSE The adsorption isotherms may reveal interaction processes involved
value of 1.301 compared to the other three models. However, the esti­ in Cr(VI) removal by CS/IONPs beads. The Qm value of CS/IONPs beads
mated fitted value of qe (73.40 mg/g) significantly deviated from the can be obtained from an isotherm plot, providing insight into the
experimental value (58.56 mg/g). In contrast, the PFO model demon­ adsorption performance. Adsorption isotherm models, specifically,
strated an RMSE value of 1.588 and a fitted qe value of 58.67 mg/g close Langmuir, Redlich-Peterson (R-P), Sips, and Freundlich, were employed
to the experimental qe value of 58.56 mg/g. Hence, Cr(VI) adsorption at 298.15 K. Fig. 5b shows the derived adsorption isotherm models (qe
kinetics using CS/IONPs beads followed the PFO model. It corroborates against Ce) (indicated by lines). Table 2 presents the adsorption iso­
that Cr(VI) adsorption onto the CS/IONPs beads was primarily driven by therms models equation, fitted parameters, R2, and RMSE values.
physisorption [37–39]. The rate constants for PFO (K1) and PSO (K2) Langmuir isotherm graph yielded Qm, KL, and R2 values as 345.53 mg/g,
models were determined to be 0.009 min− 1 and 0.00012 g mg min− 1, 1.1 × 10− 3 L mg− 1, and 0.98, respectively. The value of the separation
respectively. Also, the R2 values for both the PFO and PSO kinetic factor (RL) varied between 0.49 and 0.97, indicating a favorable Cr(VI)
models were calculated as 0.99. The parameters α and β of Elovich adsorption system [40]. Freundlich isotherm model constitutes a suit­
model were calculated as 0.972 mg g min− 1 and 0.052 g mg− 1, able model to represent multilayer adsorption. Freundlich isotherm is
respectively with an R2 value of 0.98. Further, the Weber-Morris model expressed in a linear form (Table 2), exhibiting n, KF, and R2 of 1.47,

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Table 2 contrast, the fitted outcomes of the Langmuir equation were used for
Parameters of adsorption isotherm models for Cr(VI) adsorption onto CS/IONPs assessing the Qm. The computed Qm of CS/IONPs beads for Cr(VI)
beads. removal was substantial, reaching 345.53 mg/g at pH 3 and 25 ◦ C, as
Isotherm Non-Linear Parameters Value RMSE shown in Table 2. Table 3 compares the achieved Qm value as calculated
model expression from Langmuir isotherm of synthesized CS/IONPs beads to those of
Langmuir Qm K L Ce Qm (mg g− 1) 345.53 7.650 other CS-based adsorbents at the optimized removal conditions. Looking
qe =
(1 + KL Ce ) KL (L mg− 1) × 10− 3
1.1 into some of the reported literature (Table 3), bare CS in powdery and
RL 0.49–0.97 flake forms does not have much Qm value for Cr(VI) adsorption. How­
R2 0.98
ever, CS-based composite (aerogel/hydrogel) achieved a higher adsor­
Freundlich 1 n 1.47 6.895
KF (mg g− 1)(mg bed mass of Cr(VI) over them than its powdered form. Further, a higher
qe = KF Cen 1.82
L− 1)1/n Qm value was attained in the case of CS-based beads, which suggested
R2 0.98 beads form as a suitable composite adsorbent of CS as compared to other
Sips qmax KS Cne s qmax (mg g− 1) 478.08 6.554 forms. The achieved Qm value (345.53 mg/g) of CS/IONPs beads in the
qe =
1 + KS Cne s KS (L mg− 1) × 10− 3
1.16
nS 0.92
present study was relatively higher than those of other CS-based beads
R2 0.98 adsorbent.
R-P KRP Ce KRP (L g− 1) 1.64 6.865 [The constants K1 and K2 represent the PFO and PSO, respectively.
qe = g
1 + αRP Ce αRP (L mg− 1)g 0.5 The desorption constant was denoted by β, whereas the initial adsorp­
g 0.4
tion rate was denoted by α. The rate constant (Ki) and intercept (C) were
R2 0.98
domains of IPD.].
[KF- Freundlich constant, KL-Langmuir constant, RL-separation fac­
1.82 (mg g− 1) (mg L− 1)1/n, and 0.98, respectively. The Sips and R-P tor, n- adsorption intensity, qmax - maximum adsorbed amount, Ks and
model is a hybrid model that involves characteristics of both Langmuir ns- Sips constants and, KRP, αRP and g- R-P constants.
and Freundlich models. The Sips isotherm parameters, specifically qmax,
Ks, and ns, were calculated to be 478.08 mg g− 1, 1.16 × 10− 3 L mg− 1, 3.2.8. Mechanism of Cr(VI) removal
and 0.92, respectively. Further, the parameters associated with the R-P The mechanisms behind the removal of Cr(VI) through CS/IONPs
model, namely KRP, αRP, and g, were determined as 1.64 L g− 1, 0.5 (L beads were investigated through analytical techniques of XPS (Fig. 6)
mg− 1) g, and 0.39, respectively. The R2 values of both (Sips and R-P) and FTIR (Fig. 7(a)), respectively. Fig. 6 displays the XPS spectra ob­
isotherm models were determined to be 0.98. tained before and after Cr(VI) adsorption. The presence of the Cr2p
The isotherm models were evaluated based on their RMSE values, as spectrum in the Cr-loaded CS/IONPs beads advocates (Fig. 6a) the
listed in Table 2. Sips model showed the lowest RMSE value (6.554), removal of Cr(VI). The XPS spectra of C1s (Fig. 6b and 6c) revealed the
followed by R-P, Freundlich, and Langmuir models, in that order. This presence of three distinct peaks at binding energies (BE) of 284.5, 286.1,
demonstrates that heterogeneous active sites over CS/IONPs beads were and 288.4 eV. These peaks were attributed to C–C, C–N, and C = O
involved in the adsorption of Cr(VI) [41]. Also, the heterogeneity functional groups [4,9,53]. This observation revealed the possible ex­
exponent (nS) value of Cr(VI) removal through CS/IONPs beads was not istence of CS groups, such as –NH2 and –OH, in CS/IONPs beads. The
equal to unity (Table 2), which confirms the occurrence of heteroge­ oxidation of the n–OH group facilitated the removal of Cr(VI) [4] and
neous adsorption [42]. This heterogeneity was due to various active thus promoted Cr(VI) removal efficiency through CS/IONPs beads.
components such as IONPs, –NH2, and –OH on the surface of CS/IONPs Moreover, in the case of CS/IONPs beads deconvoluted N1s spectra
beads. However, most of the utilized CS based adsorbents co-related well (Fig. 6d), two peaks were found at 400.9 and 402.8 eV, which were
with Langmuir isotherm model for Cr(VI) adsorption [3,15,43,44]. In assigned to –NH2, and –NH- of CS, respectively [1]. After Cr(VI)

Table 3
Reported Qm values and optimum conditions for Cr(VI) removal using CS-based adsorbents.
Adsorbent Optimized conditions Cr(VI) Qm Regeneration Anti-interference Source
Initial Temperature Doses Contact Initial Cr(VI) removal (mg/g) cycles
pH (◦ C) (g/L) time concentration (%)
(min) (mg/L)

CS powder 4 20 0.1 240 0.5 94.7 35.6 – Cl− , SO2-

4 [45]
CS flakes 3 30 13 180 30 – 22.09 – – [15]
CS-doped multiwalled 2 – – 60 – – 26.14 – – [46]
carbon nanotubes
CS-based hydrogel 4.5 25 0.83 3000 100 94.72 73.14 – – [47]
CS oligosaccharide 3 30 0.5 100 100 – 148.1 5 – [48]
hydrogel
CS-graphene oxide (GO)/ – 25 0.1 2880 0.58 – 127.4 5 – [49]
carboxymethyl Cellulose
composite aerogel
CS-modified magnetic 3 25 2.5 1440 300 >90 127 5 Na+, Ca2+, Fe3+, [50]
bamboo biochar Cl− , SO2− 3−
4 , PO4
FeS-CS-biochar composite 2 25 0.2 360 500 100 88.18 5 Cl− , SO2−
4 [51]
Polyethyleneimine- 6 29 1 30 – 98 199.8 5 – [52]
activated carbon-Fe3O4-
CS/polyvinyl alcohol
beads
Fe2O3-GO/CS beads 2 45 0.9 3000 80 94.3 141.50 5 Ca2+, Mg2+, [38]
Zn2+, NO3− , Cl− ,
SO2−
4 , PO4 ,
3−

CS/IONPs beads 3 25 2.5 480 150 98.71 345.53 4 Na+, Ca2+, This
Mg2+, PO3- 2-
4 , SO4 , study
NO−3 , Cl−

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Fig. 6. (a) XPS survey spectra of fresh and used CS/IONPs beads, deconvoluted XPS high-resolution spectrum for (b and c) C1s, (d and e) N1s, (f and g) O1s, (h and i)
Fe2p and (j) Cr2p.

adsorption (Fig. 6e), the –NH2 functional group peak was shifted, which CS were assigned to the band at 2929 cm− 1 [1]. The –NH2 groups
validated their participation in Cr species removal. Further, protonation bending was observed to the bands at 1640 and 1565 cm− 1 [58]. The
of –NH2 to NH+ 3 was confirmed through a deconvoluted peak (Fig. 6e) at band at 1565 cm− 1 became weaker and broader in the spectrum of Cr
402 eV [17]. The peaks at 532 and 533.9 eV of O1s in CS/IONPs beads (VI) adsorbed CS/IONPs beads, which could be ascribed to the formation
(Fig. 6f) were ascribed to C-OH and -O-C-O, respectively [4,17,54]. After of a complex between –NH2 and Cr(III) [4]. The –CH2 bending was
Cr(VI) adsorption (Fig. 6g), the deconvoluted peak of C-OH was shifted associated with a robust 1383 cm− 1 band [59]. At 1315 cm− 1, the ab­
to 532.6 eV, while the peak for -O-C-O remained unchanged. This pro­ sorption band corresponded to amide III (C-N stretching) [60]. The
posed that C-OH groups were involved in Cr(VI) removal through CS/ secondary alcohol groups’ C-O signals were observed at 1068 and 1162
IONPS beads. Prior to Cr(VI) adsorption (Fig. 6h), the BE peaks at 709.2, cm− 1 [1]. The iron oxides in CS/IONPs beads corresponded to the bands
712.4, and 721.2 eV were associated with Fe2+ and Fe3+ in CS/IONPs with wavenumbers of 709, 892, and 535 cm− 1 [4,9,61]. Further, these
beads, respectively [17]. However, after adsorption of Cr(VI) (Fig. 6i), bands were weakened after Cr(VI) adsorption (CS/IONPs-Cr beads),
the Fe2+ peak disappeared (oxidized to Fe3+), and Fe3+ peaks were which was attributed as a result of secondary alcohol groups chelated
shifted to higher BE (713.2 and 723.2 eV), along with additional peaks with Fe3+ [1]. These observations imply that IONPs in CS/IONPs beads
aroused for Fe3+ at 710.3 and 715.4 eV, respectively [55]. These find­ were implicated in Cr(VI) removal.
ings demonstrated that Cr(VI) adsorption through CS/IONPs beads in­ To facilitate a more comprehensive examination of Cr(VI) ions
volves Fe2+ and Fe3+. Furthermore, the deconvoluted peaks in the Cr2p removal mechanism, differences in Cr species concentrations,
spectrum (Fig. 6j) at BE of 577.7 and 587.2 eV corresponded to Cr(III) comprising Cr(VI), Cr(III), and Cr(tot), were also observed over the
[4,56], signifying the reduction of Cr(VI). The peaks observed at 582.6 contact time (480 min) of Cr(VI) removal through CS/IONPs beads
and 590 eV were attributed to Cr(VI) [9,57], which advocated the (Fig. 7 (b)). During the first 300 min of contact time, Cr(tot) concen­
adsorption of Cr(VI) occurred through CS/IONPs beads. Cr(III) also tration decreased significantly before levelling off at a plateau (480
could be removed by co-precipitation with Fe(III), forming a solid min). The observed fast rise in Cr(III) concentration suggested a signif­
solution-like species. icant quantity of Cr(VI) species reduced through reaction with Fe2+ ions
The stretched vibrations of O-H and N-H (Fig. 7(a)) caused the broad (Eqs. (7) and (8) during the initial stages of Cr(VI) removal. Afterwards,
band between 3300–3450 cm− 1 observed in CS/IONPs beads [4]. The CS/IONPs active sites quickly re-adsorbed the produced Cr(III) ions,
methyl (–CH3) and methylene (–CH2) groups C-H stretched vibration in leading to a plateau for Cr(III) concentrations. Nevertheless, Cr(III)

Fig. 7. (a) FTIR spectra of CS/IONPs and after Cr(VI) adsorption (CS/IONPs-Cr) beads and (b) Measured Cr(tot), Cr(VI), and Cr(III) concentrations within a contact
period of 480 min of Cr(VI) species with CS/IONPs beads.

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A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

adsorption over CS/IONPs beads reached saturation within 300 min. As

a result, the steady reduction reaction of Cr(VI) to Cr(III) led to an in­
crease in the concentrations of Cr(III) from 300 min, ultimately reaching
nearly the saturation concentration of 34 mg/L at pH 3.
Furthermore, Cr(tot) concentration exhibited a notable decline
following a similar pattern as Cr(VI). This observation suggests that
during the contact period of 480 min, more significant Cr(VI) ions un­
derwent adsorption onto the CS/IONPs beads surface rather than being
condensed to Cr(III). According to the above explanations, Cr(VI)
removal mechanisms through CS/IONPs beads involved adsorption and
reduction of Cr species through various surface and interior moieties of
the formed beads, as described in Fig. 8.

3.2.9. Reusability of CS/IONPs beads

The ability of a saturated adsorbent to be well regenerated and
reused impacts its practical usefulness. The present investigation in­
volves the assessment of Cr(VI) desorption using NaOH solution for four
successive cycles. The findings indicate that the removal % remained
consistent (98 %) for up to two cycles but dropped to 83 % in the final Fig. 9. Variations in Cr(VI) removal and desorption % during four cycles of
(4th) adsorption cycle (Fig. 9). The desorption of Cr(VI) was about 99.8 repeated adsorption and desorption of CS/IONPs beads in aqueous solution.
% up to two desorption cycles. It started to decline with more desorp­
tion/adsorption cycles and reached 48 % in the 4th desorption cycle 4. Conclusions
(Fig. 9). All elements (O, C, N, and Fe) except Cr were present in EDS
image mapping of used CS/IONPs beads (Figure S12). It indicates In the present investigation, bio-based IONPs were immobilized and
complete desorption of Cr(VI) ions from the beads in NaOH solution up entrapped within the CS matrix to synthesize reusable bi-functional
to two desorption cycles. The conversion of Cr(VI) to Cr(III) also composite CS/IONPs adsorbent. The stability of CS/IONPs beads was
declined beyond two desorption/adsorption cycles (Figure S13). The significantly affected by the pH of the aqueous solution, and composite
incomplete desorption of Cr(VI) species from CS/IONPs beads resulted beads were found to be stable above pH ≥ 3. The used CS/IONPs
in the unrecoverable occupation of adsorptive sites over the beads and adsorbent retained its morphological and structural attributes after 4
decreased the adsorbent (CS/IONPs beads) and adsorbate (Cr(VI)) in­ cycles of reusability tests. CS/IONPs exhibited a maximum 98.71 %
teractions [21] after the first two desorption/adsorption cycles. As a removal at the optimized initial pH of 3, CS/IONPs dose of 2.5 g/L, and
consequence, the removal percentage of Cr(VI) was reduced in subse­ temperature of 25 ◦ C with an initial Cr(VI) concentration of 150 mg/L.
quent adsorption cycles. Also, the changes in C1s, O1s and N1s signals Co-existing cations (Na+, Ca2+, Mg2+) did not significantly affect Cr(VI)
(Fig. 6c, 6e and 6 g) of CS/IONPs beads after Cr(VI) adsorption exposed removal efficiency; however, PO3− 2−
4 and SO4 anions interfered with Cr
the partial oxidation of adsorbent beads [62]. This passivation (VI) adsorption owing to complexation with Fe3+ species in CS/IONPs.
contributed towards the progressive degradation of the CS/IONPs beads Langmuir isotherm suggests that CS/IONPs composite beads could
during subsequent adsorption cycles, which decreased the Cr(VI) adsorb as high as 345 mg Cr(VI)/g CS/IONPs. The change in Gibbs free
removal efficacy upon its reusability (Fig. 9). Figure S14 reveals that a energy, heat of adsorption, and entropy of Cr(VI) adsorption was found
very small amount of iron (<0.55 mg/L) was leached from IONPs into to be − 14.8 to − 13.18 KJ mol− 1, − 29.35 KJ mol− 1, and − 48.55 J mol− 1
the aqueous solution during subsequent adsorption cycles and followed K− 1, respectively.
a decreased trend, with the lowest in the last (4th) cycle. It implies that Cr(VI) species were removed by electrostatic interactions between
the IONPs remained closely packed in the CS matrix during subsequent protonated NH+ 3 and OH2 functional groups of CS/IONPs beads. Fe(II)
+

cycles of Cr(VI) adsorption through CS/IONPs beads. These findings and Fe(III) synergized Cr(VI) removal through Cr(VI) reduction to Cr(III)
suggest that CS/IONPs beads can undergo facile regeneration using and Cr(III)/Fe(III) co-precipitation along with Cr(III) surface complex­
NaOH. Therefore, CS/IONPs beads are regarded as a suitable adsorbent ation with the –NH2 group. CS/IONPs beads exhibited a gradual decay in
candidate for removing Cr(VI) in real applications. Cr(VI) removal within 5 cycles of adsorption, and a decrease of 15.7 % in

Fig. 8. The proposed Cr(VI) elimination approach uses synthesized CS/IONPs beads.

10
A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

Cr(VI) removal was observed using the re-used adsorbent. Therefore, [12] A. Jawed, V. Saxena, L.M. Pandey, Engineered nanomaterials and their surface
functionalization for the removal of heavy metals: a review, J. Water Process. Eng.
CS/IONPs are a potential bi-functional composite adsorbent for Cr(VI)
33 (2020) 101009.
removal and Cr(VI) detoxification to Cr(III). [13] A. Jawed, S. Sharma, A.K. Golder, L.M. Pandey, Plant-polyphenol-mediated
synthesis of iron oxide nanomaterials for heavy metal removal: a review, New
Trends in Removal of Heavy Metals from Industrial Wastewater (2021) 115–129.
CRediT authorship contribution statement [14] I. Maamoun, O. Falyouna, R. Eljamal, M.F. Idham, K. Tanaka, O. Eljamal, Bench-
scale injection of magnesium hydroxide encapsulated iron nanoparticles (nFe0@
Aquib Jawed: Writing – review & editing, Writing – original draft, Mg(OH)2) into porous media for Cr (VI) removal from groundwater, Chem. Eng. J.
451 (2023) 138718.
Methodology, Investigation, Conceptualization. Animes K. Golder: [15] Y.A. Aydın, N.D. Aksoy, Adsorption of chromium on chitosan: Optimization,
Writing – original draft, Supervision, Formal analysis, Conceptualiza­ kinetics and thermodynamics, Chem. Eng. J. 151 (1–3) (2009) 188–194.
tion. Lalit M. Pandey: Writing – review & editing, Writing – original [16] T. Liu, Z.-L. Wang, L. Zhao, X. Yang, Enhanced chitosan/Fe0-nanoparticles beads
for hexavalent chromium removal from wastewater, Chem. Eng. J. 189 (2012)
draft, Supervision, Resources, Formal analysis, Conceptualization.
196–202.
[17] Y. Liu, H. Shan, Y. Pang, H. Zhan, C. Zeng, Iron modified chitosan/coconut shell
activated carbon composite beads for Cr (VI) removal from aqueous solution, Int. J.
Declaration of competing interest Biol. Macromol. 224 (2023) 156–169.
[18] T. Liu, L. Zhao, D. Sun, X. Tan, Entrapment of nanoscale zero-valent iron in
chitosan beads for hexavalent chromium removal from wastewater, J. Hazard.
The authors declare that they have no known competing financial Mater. 184 (1–3) (2010) 724–730.
interests or personal relationships that could have appeared to influence [19] T. Kekes, G. Kolliopoulos, C. Tzia, Hexavalent chromium adsorption onto
the work reported in this paper. crosslinked chitosan and chitosan/β-cyclodextrin beads: Novel materials for water
decontamination, J. Environ. Chem. Eng. 9 (4) (2021) 105581.
[20] T. Kekes, C. Tzia, Adsorption of indigo carmine on functional chitosan and
Data availability β-cyclodextrin/chitosan beads: Equilibrium, kinetics and mechanism studies,
J. Environ. Manage. 262 (2020) 110372.
[21] M. Vakili, S. Deng, T. Li, W. Wang, W. Wang, G. Yu, Novel crosslinked chitosan for
Data will be made available on request. enhanced adsorption of hexavalent chromium in acidic solution, Chem. Eng. J. 347
(2018) 782–790.
Acknowledgements [22] S.C. Dey, M. Al-Amin, T.U. Rashid, M.Z. Sultan, M. Ashaduzzaman, M. Sarker, S.
M. Shamsuddin, Preparation, characterization and performance evaluation of
chitosan as an adsorbent for remazol red, Int. J. Latest Res. Eng. Technol 2 (2)
The authors acknowledge the Centre For the Environment, Depart­ (2016) 52–62.
ment of Biosciences and Bioengineering, and Department of Chemical [23] J. Kurczewska, Chitosan-montmorillonite hydrogel beads for effective dye
adsorption, J. Water Process. Eng. 48 (2022) 102928.
Engineering, Indian Institute of Technology (IIT) Guwahati. The authors [24] Z. Anfar, H. Ait Ahsaine, M. Zbair, A. Amedlous, A. Ait El Fakir, A. Jada, N., El
would like to express their gratitude to the Central Instrument Facility, Alem, Recent trends on numerical investigations of response surface methodology
IIT Guwahati, for granting access to several facilities needed for the for pollutants adsorption onto activated carbon materials: a review, Crit. Rev.
Environ. Sci. Technol. 50 (10) (2020) 1043–1084.
current study. [25] Y. He, J. Chen, J. Lv, Y. Huang, S. Zhou, W. Li, Y. Li, F. Chang, H. Zhang,
T. Wågberg, Separable amino-functionalized biochar/alginate beads for efficient
removal of Cr (VI) from original electroplating wastewater at room temperature,
Appendix A. Supplementary data
J. Clean. Prod. 373 (2022) 133790.
[26] M. Hassan, Y. Liu, R. Naidu, J. Du, F. Qi, S.W. Donne, M.M. Islam, Mesoporous
Supplementary data to this article can be found online at https://doi. biopolymer architecture enhanced the adsorption and selectivity of aqueous heavy-
org/10.1016/j.cej.2023.148411. metal ions, ACS Omega 6 (23) (2021) 15316–15331.
[27] S. Chatterjee, M.W. Lee, S.H. Woo, Enhanced mechanical strength of chitosan
hydrogel beads by impregnation with carbon nanotubes, Carbon 47 (12) (2009)
References 2933–2936.
[28] S.-F. Wang, L. Shen, W.-D. Zhang, Y.-J. Tong, Preparation and mechanical
properties of chitosan/carbon nanotubes composites, Biomacromolecules 6 (6)
[1] J. Lu, K. Xu, J. Yang, Y. Hao, F. Cheng, Nano iron oxide impregnated in chitosan
(2005) 3067–3072.
bead as a highly efficient sorbent for Cr (VI) removal from water, Carbohydr.
[29] M.M.A. Aslam, W. Den, H.-W. Kuo, Encapsulated chitosan-modified magnetic
Polym. 173 (2017) 28–36.
carbon nanotubes for aqueous-phase CrVI uptake, J. Water Process. Eng. 40 (2021)
[2] S. Wang, Y. Liu, Y. Hu, W. Shen, A magnetic MIL-125-NH2@ chitosan composite as
101793.
a separable adsorbent for the removal of Cr (VI) from wastewater, Int. J. Biol.
[30] Z. Wang, Y. Wang, S. Cao, S. Liu, Z. Chen, J. Chen, Y. Chen, J. Fu, Fabrication of
Macromol. 226 (2023) 1054–1065.
core@ shell structural Fe-Fe2O3@PHCP nanochains with high saturation
[3] L. Li, Q. Liao, B. Hou, C. He, J. Liu, B. Li, M. Yu, Y. Liu, B. Lai, B. Yang, Synchronous
magnetization and abundant amino groups for hexavalent chromium adsorption
reduction and removal of hexavalent chromium from wastewater by modified
and reduction, J. Hazard. Mater. 384 (2020) 121483.
magnetic chitosan beads, Sep. Purif. Technol. 304 (2023) 122363.
[31] S. Chatterjee, S. Mahanty, P. Das, P. Chaudhuri, S. Das, Biofabrication of iron oxide
[4] J.B. Lu, B.X. Li, W.L. Li, X.T. Zhang, W. Zhang, P. Zhang, R.X. Su, D.F. Liu, Nano
nanoparticles using manglicolous fungus Aspergillus niger BSC-1 and removal of Cr
iron oxides impregnated chitosan beads towards aqueous Cr(VI) elimination:
(VI) from aqueous solution, Chem. Eng. J. 385 (2020) 123790.
Components optimization and performance evaluation, Colloids Surf. a:
[32] A. Mishra, P. Tiwari, L.M. Pandey, Surface, interfacial and thermodynamic aspects
Physicochem. Eng. Asp. 625 (2021) 126902.
of the Rhamnolipid-salt systems, J. Mol. Liq. 122245 (2023).
[5] M. Bhaumik, A. Maity, V. Srinivasu, M.S. Onyango, Removal of hexavalent
[33] R. Verma, L.M. Kundu, L.M. Pandey, Enhanced melanoidin removal by amine-
chromium from aqueous solution using polypyrrole-polyaniline nanofibers, Chem.
modified Phyllanthus emblica leaf powder, Bioresour. Technol. 339 (2021)
Eng. J. 181 (2012) 323–333.
125572.
[6] S.K. Sharma, B. Petrusevski, G. Amy, Chromium removal from water: a review,
[34] E.C. Lima, A. Hosseini-Bandegharaei, J.C. Moreno-Piraján, I. Anastopoulos,
J. Water Supply: Res. Technol. 57 (8) (2008) 541–553.
A critical review of the estimation of the thermodynamic parameters on adsorption
[7] H. Wang, D. Zhong, Y. Xu, H. Chang, H. Shen, C. Xu, J. Mou, N. Zhong, Enhanced
equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for
removal of Cr (VI) from aqueous solution by nano-zero-valent iron supported by
calculation of thermodynamic parameters of adsorption, J. Mol. Liq. 273 (2019)
KOH activated sludge-based biochar, Colloids Surf. a: Physicochem. Eng. Asp. 651
425–434.
(2022) 129697.
[35] H.N. Tran, E.C. Lima, R.-S. Juang, J.-C. Bollinger, H.-P. Chao, Thermodynamic
[8] S. Yu, Y. Yang, K. Kuroda, J. Pu, R. Guo, L.-A. Hou, Selective removal of Cr (VI)
parameters of liquid–phase adsorption process calculated from different
using polyvinylpyrrolidone and polyacrylamide co-modified MoS2 composites by
equilibrium constants related to adsorption isotherms: A comparison study,
adsorption combined with reduction, Chin Chem Lett (2023) 109130.
J. Environ. Chem. Eng. 9 (6) (2021) 106674.
[9] A. Jawed, A.K. Golder, L.M. Pandey, Synthesis of iron oxide nanoparticles
[36] A. Jawed, L.M. Pandey, Application of bimetallic Al-doped ZnO nano-assembly for
mediated by Camellia sinensis var. Assamica for Cr (VI) adsorption and
heavy metal removal and decontamination of wastewater, Water Sci. Technol. 80
detoxification, Bioresour. Technol. 376 (2023) 128816.
(11) (2019) 2067–2078.
[10] Z. Wang, L. Qiu, Y. Huang, M. Zhang, X. Cai, F. Wang, Y. Lin, Y. Shi, X. Liu,
[37] S. Koushkbaghi, A. Zakialamdari, M. Pishnamazi, H.F. Ramandi, M. Aliabadi,
Alcohothermal synthesis of sulfidated zero-valent iron for enhanced Cr (VI)
M. Irani, Aminated-Fe3O4 nanoparticles filled chitosan/PVA/PES dual layers
removal, Chin Chem Lett (2023) 109195.
nanofibrous membrane for the removal of Cr (VI) and Pb (II) ions from aqueous
[11] D. Xu, Y. Huang, Q. Ma, J. Qiao, X. Guo, Y. Wu, A 3D porous structured cellulose
solutions in adsorption and membrane processes, Chem. Eng. J. 337 (2018)
nanofibrils-based hydrogel with carbon dots-enhanced synergetic effects of
169–182.
adsorption and photocatalysis for effective Cr (VI) removal, Chem. Eng. J. 456
(2023) 141104.

11
A. Jawed et al. Chemical Engineering Journal 481 (2024) 148411

[38] H. Shan, C. Zeng, C. Zhao, H. Zhan, Iron oxides decorated graphene oxide/chitosan globules with high structure stability in liquid and extremely high adsorption
composite beads for enhanced Cr (VI) removal from aqueous solution, Int. J. Biol. ability, ACS Sustain. Chem. Eng. 7 (9) (2019) 8775–8788.
Macromol. 172 (2021) 197–209. [50] H. Zhang, R. Xiao, R. Li, A. Ali, A. Chen, Z. Zhang, Enhanced aqueous Cr (VI)
[39] I. Herath, P. Kumarathilaka, M.I. Al-Wabel, A. Abduljabbar, M. Ahmad, A. removal using chitosan-modified magnetic biochars derived from bamboo
R. Usman, M. Vithanage, Mechanistic modeling of glyphosate interaction with rice residues, Chemosphere 261 (2020) 127694.
husk derived engineered biochar, Microporous Mesoporous Mater. 225 (2016) [51] Y. Yang, Y. Zhang, G. Wang, Z. Yang, J. Xian, Y. Yang, T. Li, Y. Pu, Y. Jia, Y. Li,
280–288. Adsorption and reduction of Cr (VI) by a novel nanoscale FeS/chitosan/biochar
[40] S. Sharma, A. Hasan, N. Kumar, L.M. Pandey, Removal of methylene blue dye from composite from aqueous solution, J. Environ. Chem. Eng. 9 (4) (2021) 105407.
aqueous solution using immobilized Agrobacterium fabrum biomass along with [52] S. Singh, E. Arputharaj, H.-U. Dahms, A.K. Patel, Y.-L. Huang, Chitosan-based
iron oxide nanoparticles as biosorbent, Environ. Sci. Pollut. Res. 25 (2018) nanocomposites for removal of Cr (VI) and synthetic food colorants from
21605–21615. wastewater, Bioresour. Technol. 351 (2022) 127018.
[41] F. Zhao, E. Repo, D. Yin, L. Chen, S. Kalliola, J. Tang, E. Iakovleva, K.C. Tam, [53] A. Vasilev, M. Efimov, G. Bondarenko, V. Kozlov, E. Dzidziguri, G. Karpacheva,
M. Sillanpaa, One-pot synthesis of trifunctional chitosan-EDTA-β-cyclodextrin Thermal behavior of chitosan as a carbon material precursor under IR radiation,
polymer for simultaneous removal of metals and organic micropollutants, IOP Publishing, IOP Conf. Ser. Mater. Sci. Eng., 2019, p. 012002.
Scientific Reports 7 (1) (2017) 15811. [54] K. Wang, Q. Liu, Adsorption of phosphorylated chitosan on mineral surfaces,
[42] J. Wang, X. Guo, Adsorption isotherm models: classification, physical meaning, Colloids Surf. a: Physicochem. Eng. Asp. 436 (2013) 656–663.
application and solving method, Chemosphere 258 (2020) 127279. [55] A. Grosvenor, B. Kobe, M.C. Biesinger, N. McIntyre, Investigation of multiplet
[43] T.L. Nguyen, A. Ayub, A. Anam, A.M. Aljuwayid, S.W. Alwash, R. Abbass, A.A. splitting of Fe 2p XPS spectra and bonding in iron compounds, Surf Interface Anal
K. Ruhaima, E. Potrich, M. Sillanpaa, S. Gul, Fabrication of ZnO decorated porous 36 (12) (2004) 1564–1574.
chitosan beads for the sustainable bioremediation of Cr (VI) contaminated water, [56] K. Djebaili, Z. Mekhalif, A. Boumaza, A. Djelloul, XPS, FTIR, EDX, and XRD analysis
J. Environ Chem. Eng. (2023) 110445. of Al 2 O 3 scales grown on PM2000 alloy, J Spectrosc 2015 (2015).
[44] X. Liu, Y. Zhang, Y. Liu, T.a. Zhang, Magnetic red mud/chitosan based [57] Y. Chen, D. An, S. Sun, J. Gao, L. Qian, Reduction and removal of chromium VI in
bionanocomposites for adsorption of Cr (VI) from aqueous solutions: synthesis, water by powdered activated carbon, Materials 11 (2) (2018) 269.
characterization and adsorption kinetics, Polym. Bull. 80 (2) (2023) 2099–2118. [58] R. Heacock, L. Marion, The infrared spectra of secondary amines and their salts,
[45] C. Jung, J. Heo, J. Han, N. Her, S.-J. Lee, J. Oh, J. Ryu, Y. Yoon, Hexavalent Can. J. Chem. 34 (12) (1956) 1782–1795.
chromium removal by various adsorbents: powdered activated carbon, chitosan, [59] M. Boulet-Audet, F. Vollrath, C. Holland, Identification and classification of silks
and single/multi-walled carbon nanotubes, Sep. Purif. Technol. 106 (2013) 63–71. using infrared spectroscopy, J. Exp. Biol. 218 (19) (2015) 3138–3149.
[46] Ş. Parlayıcı, E. Pehlivan, Removal of chromium (VI) from aqueous solution using [60] E.M. Dahmane, M. Taourirte, N. Eladlani, M. Rhazi, Extraction and
chitosan doped with carbon nanotubes, Mater. Today: Proc. 18 (2019) 1978–1985. characterization of chitin and chitosan from Parapenaeus longirostris from
[47] P.B. Vilela, A. Dalalibera, E.C. Duminelli, V.A. Becegato, A.T. Paulino, Adsorption Moroccan local sources, Int. J. Polym. Anal 19 (4) (2014) 342–351.
and removal of chromium (VI) contained in aqueous solutions using a chitosan- [61] V. Vats, G. Melton, M. Islam, V.V. Krishnan, FTIR spectroscopy as a convenient tool
based hydrogel, Environ. Sci. Pollut. Res. 26 (2019) 28481–28489. for detection and identification of airborne Cr (VI) compounds arising from arc
[48] J. Mei, H. Zhang, Z. Li, H. Ou, A novel tetraethylenepentamine crosslinked chitosan welding fumes, J. Hazard. Mater. 448 (2023) 130862.
oligosaccharide hydrogel for total adsorption of Cr (VI), Carbohydr. Polym. 224 [62] C. Shen, H. Li, Y. Wen, F. Zhao, Y. Zhang, D. Wu, Y. Liu, F. Li, Spherical Cu2O-
(2019) 115154. Fe3O4@ chitosan bifunctional catalyst for coupled Cr-organic complex oxidation
[49] T. Huang, Y.-W. Shao, Q. Zhang, Y.-F. Deng, Z.-X. Liang, F.-Z. Guo, P.-C. Li, and Cr (VI) capture-reduction, Chem. Eng. J. 383 (2020) 123105.
Y. Wang, Chitosan-cross-linked graphene oxide/carboxymethyl cellulose aerogel

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