International Journal of Biological Macromolecules 275 (2024) 133561

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International Journal of Biological Macromolecules

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

Efficient removal of cationic dyes using lemon peel-chitosan hydrogel

composite: RSM-CCD optimization and adsorption studies
Triparna Das , Devendra K. Patel *
Analytical Chemistry Division (ASSIST), CSIR-Indian Institute of Toxicology Research, (CSIR-IITR), Vishvigyan Bhawan, 31, Mahatma Gandhi Marg, Lucknow 226001,
Uttar Pradesh, India
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India

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

Keywords: The most prominent and easily identifiable factor of water purity is its colour, which may be both physically
Lemon peel- chitosan hydrogel undesirable, and act as an alert towards potential environmental contamination. The current study describes the
RSM-CCD optimum synthesis technique for Lemon Peel-Chitosan hydrogel using the Response Surface Methodology inte­
Adsorption
grated Central composite Design (RSM-CCD). This adsorbent is both environmentally friendly and cost-effective.
The hydrogel exhibited a maximal dye removal capacity of 24.984, 24.788, 24.862, 23.483, 24.409, and 24.726
mg g− 1, for 10 mg L− 1 aqueous medium of Safranin O, Methylene blue, Basic fuchsin, Toluidine blue, Brilliant
green and Crystal violet, respectively. The adsorption kinetics and isotherm data suggest that the Pseudo second-
order kinetic and Freundlich adsorption isotherm models precisely represent the respective behaviour of all the
dyes. The thermodynamic viability of the process is determined by the values of ΔG, ΔH, and ΔS. The probable
mechanism of adsorption was the electrostatic interaction between the dye molecules and the hydrogel. The
regenerated hydrogel had removal efficiencies of over 80 % even after enduring six cycles. Hence, the excep­
tional recyclability and utility of the adsorbent show their sustainability for wastewater treatment in textile
factories.

1. Introduction issues such as mortality of aquatic species, as well as the formation of

unpleasant odours.[4,5] Consequently, it becomes essential to remove
Water is the most abundant natural resource found on Earth. How­ dyes from waste effluents before their release into rivers and other
ever, just a mere 3 % of the existing water reserves are classified as waterways.[6]
freshwater. Less than one-third of this freshwater is suitable for various Various conventional techniques are employed for the removal of
residential uses, crop cultivation, and manufacturing processes.[1] As dyes from water, including adsorption, membrane filtration, ion ex­
the water demand continues to rise significantly, the availability of change, photochemical methods, electrochemical destruction, and
freshwater is being depleted due to an escalating level of pollution, anaerobic bioremediation systems.[7] Among these methods, adsorp­
resulting in water scarcity for modern society.[2] The discharge of tion is regarded as a highly effective process for thoroughly eliminating
wastewater from industries such as dye, paint, paper, textile, and elec­ dyes from wastewater and is primarily attributed to its facile execution
troplating comprising hazardous substances, including dyes and metal and cost efficiency, which surpasses the alternative approaches.[8]
ions, has the potential to cause water pollution in many aquatic eco­ Hydrogels are recognized as a promising adsorbent for the remediation
systems leading to a range of health and environmental issues.[3] The of various aquatic contaminants as these materials are hydrophilic,
presence of extremely low levels, as low as 10 ppm, of dyes in water insoluble, and have a cross-linked polymer structure that offers an
results in a visible sign of a distinct colour, making it unsuitable for outstanding ability to swell as well as allow them to absorb significant
everyday life. The consumption of water that is contaminated by toxic amounts of aqueous solutions within their intricate three-dimensional
substances can cause several adverse health effects such as vomiting, networks.[9,10] Hydrogels exhibit a wide range of beneficial features,
mutation, cancer, respiratory difficulties, diarrhoea, ocular irritation, including rapid swelling kinetics, adjustable surface characteristics such
nausea, shock, cyanosis, jaundice, tissue necrosis and environmental as charge and functionality, efficient diffusion processes, expansive

* Corresponding author.
E-mail address: [email protected] (D.K. Patel).

https://doi.org/10.1016/j.ijbiomac.2024.133561
Received 4 March 2024; Received in revised form 13 June 2024; Accepted 28 June 2024
Available online 1 July 2024
0141-8130/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

surface area, controllable pore structure, permeability catalysis, rapid (AMPS), N, N′-methylenebisacrylamide (MBA) were procured from
kinetics, thermal stability, intriguing acid/base properties, and hydro­ Sigma Aldrich (USA). All the reagents were of analytical grade. Safranin
philicity.[11,12] Concerning water treatment applications, it has been O, Methylene blue, Basic fuchsin, Toluidine blue, Brilliant green and
observed that hydrogels have high efficacy in effectively containing a Crystal violet were purchased from Sisco Research Laboratories, India.
wide range of organic and inorganic aqueous pollutants such as metal All solutions were prepared using deionized water and it was provided
ions, harmful dyes, and hazardous pharmaceutical waste.[13] by the institutional water unit (Milli-Q, Millipore, Billerica, MA, USA).
In recent times, biopolymer-based hydrogel has become an emerging
adsorbent material due to its eco-friendly attributes. The growing de­ 2.2. Pre-treatment of lemon peel powder
mand for eco-friendly products has led to the development of affordable
natural adsorbents from agricultural waste, which are abundant and The fresh LP was cut into small pieces for easy drying and rinsed with
require minimal processing costs.[14] Numerous studies have been excess water three times. The peel was dried in the oven at 80 ± 5 ◦ C
conducted to synthesize biopolymers by incorporating synthetic mono­ overnight and made into powder using a grinder. It was further filtered
mers with naturally derived materials, including chitosan[15], starch using a 60-mesh sieve and stored in a desiccator at ambient temperature
[16], alginate[17], and pectin[18] to develop environmentally friendly, for further experiments. The LP was pre-treated with CTAB to improve
non-toxic hydrogels that are suitable with human use. These hydrogels its adsorption properties. 10 g of lemon peel powder was added into 100
are usually generated using copolymerization/cross-linking free-radical mL of 1 % CTAB solution and agitated for 30 min at 500 rpm. The
polymerizations, chemical reactions, and ionizing radiations.[19] materials were passed through the Whatman filter paper and rinsed with
Agricultural wastes have achieved significant acceptance as adsor­ double distilled water until the water was bromine-free. The solid res­
bents due to their high accessibility and cost-effectiveness, making them idue was subsequently dehydrated in an oven at a temperature of 100 ±
comparable to other adsorbents.[20] In recent studies, various agricul­ 5 ◦ C for a duration of 6 h and placed in a desiccator for storage. Before
tural sorbents were utilized including pineapple stem[21], banana bark the synthesis of hydrogel, the lemon peel powder coated with CTAB was
and orange peel[22], rice husk[23], grapefruit peel[24], tea waste[25], homogenized using an agate mortar and pestle.
mango and neem bark[26] and wheat straw[27] to evaluate their effi­
cacy in removing dyes. Fruit peels primarily comprise cellulose, pectin, 2.3. Experimental design
hemicelluloses, lignin, chlorophyll, pigments, and other low molecular
weight hydrocarbons and act as an adsorbent, although they are sus­ To combat the complications resulting from conventional optimiza­
ceptible to enzymatic degradation and face difficulties in their prepa­ tion methods, RSM has been used as a statistical approach. “Statistica”
ration procedure.[28] software was used for screening significant variables keeping % swelling
Dyes are one of the most prevalent pollutants in industrial effluent, as a response variable and creating a response surface graph for further
having severe negative impacts on sustainable ecosystems because of analysis. Experimental conditions were optimized using Plackett Bur­
their durable toxicity, environmental persistence, mutagen and bio­ man Design (PBD) and Central Composite Design (CCD). Lemon Peel
accumulation.[29] The presence of dyes, even in small quantities, hin­ amount (1: 100–250 mg), chitosan amount (2: 50–100 mg), monomer
ders the absorption of sunlight into water, resulting in a significant concentration (3: 1–3 mL), crosslinker concentration (4: 0.005–0.03 g)
decrease in dissolved oxygen levels leading to substantial health hazards and temperature (5: 55–65 ◦ C) was selected as independent variables
to aquatic organisms.[30] Dyes can stimulate anaerobic digestion, and % swelling as a response variable. The factorial model was validated
causing the generation of various carcinogenic substances that have the using analysis of variance (ANOVA) with a significance level of p < 0.05.
potential to infiltrate the food chain through aquatic organisms.[31] Non-significant elements were eliminated to minimize the model.
Nevertheless, the quantity of dye being discharged into various water Regression coefficient significance was assessed using half-normal and
sources remains substantial. As an example, an annual production of Pareto charts. The optimal % swelling was determined by three elements
roughly 7 × 105 tons of various reactive dyes occurs, with approximately inscribed central composite design. The design variables are Lemon Peel
5–10 % of these dyes being discharged into industrial wastewater.[32] (A: 100–250 mg) monomer (B: 1–3 mL), crosslinker (C: 0.005–0.03 g)
Thus, efficient separation of dyes from wastewater is crucial for pro­ concentrations with other factors held constant. The results obtained
tecting the worldwide ecological, biological, and industrial from the CCD were analysed using both a response surface model and a
environments. desirability function.
This study involved the fabrication of a hydrogel composed of lemon
peel and chitosan, intending to evaluate its adsorption capabilities for 2.4. Synthesis of lemon peel-chitosan hydrogel composite
five commonly found cationic dyes [Safranin O (SO), Methylene blue
(MB), Basic fuchsin (BF), Toluidine blue (TB), Brilliant green (BG) and 75 mg of chitosan and 175 mg of CTAB-treated lemon peel powder
Crystal violet (CV)] as these dyes are extensively utilized in the textile were taken in a 100 mL beaker. 10 mL of deionized water was added and
and paper sectors; highly soluble and has potential health risks. The the mixture was stirred for 10 mins. 0.10 g of ammonium persulfate was
lemon peel was treated with CTAB and was incorporated with chitosan added to the mixture. 2 mL of partially neutralized acrylic acid and 500
and acrylic acid (AA) to develop the hydrogel composite. Lemon peel μl of AMPS were added and stirred for 5 mins. N, N′-methyl­
and chitosan both are good adsorbents as well as serve as a supporting enebisacrylamide (0.0175 mg) was added and allowed to react for 1 h at
framework to strengthen the polymeric network of the hydrogel. The 60 ◦ C. This composite was cooled at room temperature and named LP-Ch
effect of various experimental parameters was assessed, together with Hg. Different hydrogels using untreated lemon peel, without AMPS and
adsorption isotherms, kinetics and thermodynamics to understand the chitosan were also prepared to analyse the contrast in structural prop­
fundamental mechanism of adsorption. erties and swelling efficiency of the hydrogels.

2. Experimental section 2.5. Characterization

2.1. Materials Attenuated Total Reflectance-Fourier Transform InfraRed (ATR-

FTIR) analysis was conducted using Thermo Fischer (Nicolet, iS5, USA)
The lemon peel (LP) was obtained from a local juice bar in Lucknow, FT-IR with a 400–4000 cm− 1 scanning range at 32 scans/min. Using
India. Acrylic acid and chitosan were procured from Thermo Fisher Zetasizer Nano-ZSP, Malvern, U.K., zeta potential of the adsorbent was
Scientific (India); cetyltrimethylammonium bromide (CTAB), ammo­ measured by Dynamic Light Scattering (DLS) technique for pH 2 to 12.
nium persulfate (APS), 2 -acrylamido-2-methyl-1-propane sulfonic acid Brunauer–Emmett–Teller (BET) and Barret-Joyner-Halenda (BJH)

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

techniques were used to study surface area and pore size on BELSORP diffusion models.[35]
MR-1, Osaka, Japan. A ZEISS EVO LS 15 (Germany) Scanning Electron Pseudo-first-order:
Microscope with Energy Dispersive X-ray (SEM-EDX) evaluated the
ln(qe − qt ) = lnqe − k1 t (4)
sample's surface texture and chemical composition. The crystallinity of
the sample was evaluated using Rigaku's SmartLab SE multifunctional X-
where qe (mg g− 1) is the quantity of adsorbate adsorbed at equilibrium,
ray Diffraction (XRD) machine and SmartLab Studio II software. Ther­ qt (mg g− 1) is the quantity of adsorbate adsorbed at a specific time and k1
mal stability was determined using Thermo Gravimetric Analyzer
(min− 1) is the pseudo-first-order rate constant.
(TGA), Mettler Toledo Stare, Columbus. 10 mg sample was heated to Pseudo-second-order:
1000 ◦ C at 10 ◦ C/min in a nitrogen-inert environment at 20 mL/min.
KRATOS Analytical Axis SUPRA X-ray photoelectron spectroscopy (XPS) t 1 1
= + (5)
(Japan) was used to analyse materials surface chemistry. The range of qt k2 q2e qe
electron beam energy was 80 to 200 KV and depth resolution was 2 to 8
nm. where k2 (g mg− 1 min− 1) is the pseudo-second-order rate constant.
Intra-particle diffusion:
2.6. Swelling studies qt = kdif t1/2 + C (6)

To assess the swelling kinetics of the hydrogel, 0.1 g of powder where kdif (g mg− 1 min− 1/2) represents the rate constant for intra-
hydrogel was submerged in 250 mL of deionized water at ambient particle diffusion, C (mg g− 1) is determined by evaluating the linear
temperature until it achieved the point of swelling equilibrium. The plots of qt and t1/2 and the term t1/2 refers to the half-life of the
swollen hydrogels were separated to determine their swelling behaviour adsorption.
by the following equation: Adsorption isotherms elucidate the correlation between the con­
Ws− Wd centration of a solute in a gas or liquid phase and its concentration on the
Swelling% = × 100 (1) surface of a solid adsorbent when equilibrium is reached. This provides
Wd
significant insights into adsorption, including the adsorbent's capacity,
Where dry composite weight is Wd and swollen composite weight is Ws. the intensity of the adsorbate-adsorbent interaction, and the underlying
[33] mechanisms of adsorption. The adsorption mechanism was studied
using three isotherm models: Langmuir, Freundlich, and Temkin.
2.7. Dye adsorption studies [36,37]
Langmuir adsorption isotherm equation:
The sorption experiments of dyes were conducted individually and Ce Ce 1
different parameters including contact duration, adsorbent dose, pH, = + (7)
Qe Qm KL Qm
and initial dye concentration of the solution were optimized to achieve
the maximum amount of dye removal from the aqueous solution. The Where equilibrium concentration is denoted as Ce (mg L− 1), the theo­
absorbance of all the solutions was analysed using a multimode plate retical maximum adsorption capacity is represented by Qm (mg g− 1) and
reader (Tecan, Infinite 200PRO) and the residual dye concentration was equilibrium adsorption capacity is denoted as Qe (mg g− 1). The Lang­
analysed at certain wavelengths for several dyes: 662 nm λmax for muir constant, KL, represents the affinity of the binding site.
methylene blue, 541 nm λmax for basic fuchsin, 530 nm λmax for Freundlich adsorption isotherm equation:
safranin O, 633 nm λmax for toluidine blue, 586 nm λmax for crystal
violet, and 625 nm λmax for brilliant green dyes. To assess hydrogel's 1
logQe = logKF + logCe (8)
adsorption efficacy, adsorption capacity (qe) and % removal (%RD) were n
calculated. 0.01 g of powdered hydrogel was treated with 25 mL of dye The adsorption capacity at equilibrium, denoted as Qe (mg g− 1), is
solution (10 mg L− 1) and shaken at 50 rpm for 1 h. This study comprised determined by the equilibrium concentration of the solution and it is
both individual and combined dye solutions of 10 mg L− 1. denoted as Ce (mg L− 1), KF is the Freundlich constant, and the Freund­
The adsorption capacity qe (mg g− 1) was calculated as per Eq: lich coefficient, n, are factors that respectively represent the intensity of
adsorption.
Co− Ce
qe = ×V (2) Temkin adsorption isotherm equation:
W
Qe = A + B lnCe (9)
Where Co and Ce (mg L− 1) represent dye ion concentrations before and
following adsorption respectively, whereas V (L) represents solution where Ce (mg L− 1) represents the equilibrium concentration and Qe (mg
volume and W (g) represents adsorbent weight. g− 1) represents the equilibrium adsorption capacity. Temkin constants
The % removal was evaluated as per Eq: denoting binding energy and adsorption heat, respectively, are denoted
Ci− Cf by A and B.
%RD = × 100 (3)
Ci
2.9. Thermodynamics
Where Ci is the initial dye concentration and Cf (mg L− 1) is the final dye
concentration after adsorption.[34] The influence of temperature on the adsorption of dyes was inves­
tigated at four specific temperatures: 293 K, 303 K, 313 K, and 323 K.
2.8. Adsorption kinetics, isotherm and thermodynamics
ΔG = − RT lnKd (10)
Comprehending the kinetics of adsorption is vital for enhancing
− ΔH ΔS
adsorption processes in numerous applications. The mechanism depends lnKd = + (11)
RT R
on several parameters, such as the chemical properties of the adsorbate
and adsorbent, temperature, pressure, and the concentration of the Qe
adsorbate in the environment. Adsorption kinetics have been explained Kd = (12)
Ce
through pseudo-first-order, pseudo-second-order and intraparticle

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

Where R represents the gas constant (J mol− 1 K− 1), T is the temperature 95 % probability has been employed to determine significant factors that
(K), Kd represents adsorption affinity, Qe refers to the optimal adsorption impact the swelling ability of the hydrogel.[41] The Pareto chart
capacity (mg g− 1), Ce represents the optimal concentration of dye ions (Fig. 1.) illustrates the significant factors implicated in the screening
(mg L− 1) in the solution.[38] experiment. Crosslinker was determined to be the most important factor
followed by monomer and lemon peel. Chitosan and temperature were
insignificant factors they fell below the threshold shown by the red line
2.10. Recycling on the Pareto chart. For insignificant factors, the mid value of the range,
such as 75 mg of chitosan and 60 ◦ C temperature was chosen for further
The regeneration and reusability of the hydrogel was determined investigation. The most significant factors underwent additional opti­
using a conventional technique. A 10 % solution of acetic acid was mization utilizing central composite design (CCD).
utilized to desorb all of the dyes. Following desorption, the samples were
subsequently utilized for the adsorption of dyes using optimal condi­ 3.1.2. RSM- central composite design (CCD)
tions. The potential for reusability was assessed using a UV–visible RSM, or Response Surface Methodology, is a comprehensive statis­
spectrophotometer. The regenerated adsorbent was used for six cycles to tical technique that is beneficial for identifying and improving compo­
confirm the reusability of the hydrogel. The regeneration efficiency (ER nents for synthesis. The RSM was represented by three-dimensional
%) was calculated by comparing the adsorption capacity of the latest graphs depicting the interaction between three components, as seen in
prepared adsorbents with that of regenerated adsorbents, using the eq. Fig. 2. The optimal conditions for all the parameters were determined by
(13) as follows: desirability profiling of CCD. The desirability profile for all the com­
ponents is depicted in Fig. 3, which exhibits a series of graphs for each
QR
ER = (13) independent variable. The quadratic model in CCD is established by
QF
optimizing significant parameters using the dependent and independent
where QR and QF represent the adsorbed amount of dye ions on the variables.[42] The methodology employs a factorial design, using axial
regenerated and fresh adsorbent respectively.[39] and center points to effectively model polynomials. The PBD screening
revealed three parameters to be optimized: crosslinker, monomer, and
lemon peel. These components were selected at three different levels:
3. Results and discussion
low (− 1), intermediate (0), and high (+1). CCD has a total of 2 k + 1 star
points. The star points were located at distances of +α and − α from the
3.1. Factorial design
center point, respectively. CCD offers several possibilities, and when α is
set to 1, it creates a unique scenario where star points appear at the
3.1.1. Plackett burman design (PBD)
border, leading to a total of 32 patterns. The value of “α” required to
Following the preliminary experiments, PBD was performed to
assure orthogonality and rotatability may be computed using the for­
optimize the factors that influence the swelling ability of the hydrogel.
mula α = (2k) ¼, where k is the number of variables to be screened.
PBD is highly effective for screening the significant factors among a wide
Therefore, in this particular example, the value of k is 3 and the value of
range of other factors by eliminating interactions, hence enabling esti­
α is 1.68. The CCD comprises 2 k factorial runs, 2 k axial runs, and center
mation of the primary effects using a reduced number of experimental
points (Cp). The total number of runs (N) in CCD may be calculated
runs.[40] In this experiment, the PBD approach involved fractional
using this equation: N = 2 k + 2 k + Cp. Let k represent the total number
factorial design of 2k-2 experimental runs, with k variables being tested
of factors to be screened and CP represent the number of center points
at both low and high levels. The total number of runs were 8 (25–2 = 23
(CP = 2).[43] As there are three factors for optimization, so, a total of 16
= 8) with randomly distributed 6 center points. The experiment was
(N = 23 + 2*3 + 2 = 16) experimental runs were conducted randomly, to
conducted in triplicate to mitigate any possibility of error. A total of 30
exclude the influence of unregulated variables. The responses were
runs [(8*3 = 24) + 6] were conducted. The five variables were: lemon
quantified as % swelling of the hydrogels. The data acquired from CCD
peel, chitosan, monomer, crosslinker and temperature. All the data have
were analysed using ANOVA and outcomes are shown in the
been analysed using analysis of variance (ANOVA) and the t-test with a

Fig. 1. Standardized main effect Pareto chart for PBD screening to optimize five parameters for hydrogel synthesis.

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

Fig. 2. Response surface estimation using CCD for hydrogel synthesis.

supplementary information S 01. The polynomial model's goodness of fit are interconnected to create a three-dimensional structure. The optimal
was measured using the coefficient of determination (R2) and adjusted values for the experiment were determined to be 2 mL of monomer,
R2, which were calculated to be 0.92772 and 0.81929, respectively. The 0.0175 mg of crosslinker, and 175 mg of lemon peel.
statistical analysis confirms that the model is supported by a higher
value of adjusted R2, indicating no substantial lack of fit. Furthermore, 3.2. Characterization
the suggested model accurately matches the actual experimental data.
The projected values inside the desirability function might vary from 3.2.1. Fourier transform infrared (FT-IR) analysis
unfavorable (0.0) to favorable (1.0), denoting the levels of factors that FTIR spectra of lemon peel, chitosan and LP-Ch hydrogel are shown
can provide the most favorable response based on dependent factors. in Fig. 4.A. Broad band at approximately 3300 cm− 1 is observed in
The red vertical line in the graph indicates the optimum values.[44] The lemon peel and chitosan; this band is ascribed to the O–H stretching
outcomes of CCD have been represented using the response surface vibration of hydroxyl groups in alcohols and phenols. There is an
model (RSM) and desirability profile (DP), which are derived by absence peak around 3300 cm− 1 in the LP-Ch hydrogel which means the
considering all the key interactions present in CCD. The data was ana­ -OH groups have been removed, and a bonding reaction called C-O-C has
lysed using ANOVA to identify the variables affecting the swelling ca­ taken place between the lemon peel, chitosan, and monomer.[45] The
pacity of hydrogel with a 95 % probability based on the individual band around 2900 cm− 1 is attributed to C–H stretching vibrations in
responses in supplementary table S 01. The response surface model for -CH3 and -CH2 groups, indicating the presence of lipids and organic
three factorial designs demonstrated the interaction between two factors compounds and AA copolymerization produces the bands at 2943.92
while holding the value of the third component constant. The interaction and 2899.30 cm− 1 in the synthesized hydrogel. The band around
of lemon peel and monomer while keeping the crosslinker constant in­ 1740–1710 cm− 1 is indicative of the presence of flavour compounds and
dicates that the optimal quantity of lemon peel for achieving the highest essential oils in lemon peel, as it corresponds to the C– –O stretching
swelling yield falls within the range of 180–220 mg. The lemon peel vibration of carbonyl groups in aldehydes and ketones. The -COO group
contains a significant quantity of pectin and cellulose, and its porous in AA vibrates at 1541.66 cm− 1 in the hydrogel. Bands around
structure enhances its capacity to swell. The optimal range for the 1500–1450 and 1380–1330 cm− 1 correspond to C–H bending vibra­
crosslinker was determined to be between 0.015 and 0.025 mg. This tions in aromatic compounds and methyl and methylene groups
phenomenon may be attributed to the correlation between a greater respectively.[46] Hydrogel exhibits the characteristic peak of AMPS at
concentration of crosslinks and increased rigidity of the hydrogel. 1031 cm− 1.[47]
Conversely, a lower number of crosslinks leads to a softer hydrogel that
may not effectively retain the desired analyte. Therefore, within this 3.2.2. Thermogravimetric analysis (TGA)
range, the hydrogel exhibits sufficient flexibility. The monomer volume Fig. 4.B showed that all hydrogels displayed similar mass loss pat­
ranged from 2 to 2.5 mL, with greater % swelling. This is feasible terns when the temperature rose from around 30 to 700 ◦ C. The residues
because polymer chains constitute the core of the hydrogel network and of LP-Ch Hg, LP Hg, Ch Hg, LP-Ch Hg (synthesized without utilizing

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

Fig. 3. Desirability profiles for predicted optimum value.

Fig. 4. FTIR spectra of lemon peel, CTAB treated lemon peel, chitosan, LP-Ch hydrogel (A); TGA of different hydrogels (B); Zeta potential of LP-Ch Hg at different
pH (C).

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

copolymer AMPS), and LP-Ch Hg (synthesized using untreated lemon is adequate to adsorb dyes because usually, their molecular diameter
peel) were 27.31 %, 22.29 %, 19.81 %, 23.02 %, and 27.29 % respec­ ranges from 1 to 2 nm.[48] The hydrogel had a specific surface area of
tively at 692.5 ◦ C. LP-Ch Hg and LP-Ch Hg (made with untreated lemon approximately 0.6646 m2 g− 1 and a total pore volume of 0.000455 cm3
peel) exhibited higher thermal stability compared to other synthesized g− 1 at P/P0 = 0.99. The BET plot of the hydrogel is illustrated in sup­
hydrogels, with Ch Hg showing the lowest thermal stability. plementary information S 02.

3.2.3. Zeta potential 3.2.5. XRD analysis

To assess its zeta potential, the LP-Ch hydrogel was immersed in The XRD spectra of LP-Ch hydrogel, lemon peel and chitosan indicate
acidic, neutral, and alkaline solutions. The powdered hydrogel was that the semi-crystalline structure of lemon peel and chitosan was
diluted to 0.2 wt% and agitated for 15 min and then zeta potential was destroyed due to cross-linking and grating during synthesis. Diffraction
measured in solutions of varying pH. The zeta potential consistently peak of lemon peel at 2ɵ = 22.024◦ was shifted to 20.834◦ and broad­
dropped towards negative values, as the pH climbed from 2 to 12. The ened. This broadening of the peak in the hydrogel indicates amorphous
point of zero charge (pzc) of the hydrogel was at pH = 2.28. This nature of the material which usually enhances its adsorption capacity.
experiment confirms the electrostatic interactions between hydrogel [49] The XRD spectra of lemon peel and LP-Ch hydrogel are provided in
and cationic dye molecules in a particular pH. Fig. 4.C displayed the supplementary information S 03 and S 04.
fluctuations in zeta potential of the LP-Ch hydrogel as a result of pH
modifications. 3.2.6. SEM and EDS analysis
The presence of micropores in the hydrogel becomes very prominent
3.2.4. BET analysis after adsorption since they expand significantly after adsorption.(Fig. 5.)
The hydrogel presented a mean pore diameter of 2.7419 mm, which The hydrogel's surface has a coarse and inconsistent porous texture,

Fig. 5. SEM images of LP-Ch hydrogel before (A) and after (B) adsorption; survey XPS spectra of LP-Ch hydrogel (C), deconvolution XPS peaks of C 1s (D), S 2p (E), N
1s (F), Na 1s (G) and O 1s (H) of LP-Ch hydrogel.

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

increasing the possibility of dye molecules penetrating the polymeric eV), C–N bond (398.4 eV), and N+ species (399.5 eV).The peaks
structure of LP-Ch hydrogel. The hydrogel is very dense and can accel­ observed at 1068.4 eV can be attributed to the presence of sodium (Na).
erate the quick adsorption of aqueous solutions, hence increasing the Two distinct peaks are seen for the O 1s orbital at 528.6 and 529.9 eV,
water-retention capacity of the polymer. The surface exhibited a which correlate to the presence of ester carbonyl (RCOO) and C–O
considerable number of microporous structures, leading to an increased bonds respectively.[50]
specific surface area that allowed for a greater capacity to adsorb
desirable compounds. EDS spectra of LP-Ch hydrogel before and after 3.3. Swelling test
adsorption are provided in supplementary information S 05 and S 06.
The swelling behaviour of hydrogels is crucial for understanding
3.2.7. X-ray photoelectron spectroscopy their ability to retain water, which is relevant for their application in dye
The X-ray photoelectron spectroscopy technique was used to provide adsorption. The swelling capacity of LP-Ch hydrogel was found to be
detailed information about the chemical composition of the synthesized around 39,028.6 %.
hydrogel. Fig. 5.(C–H) denotes the distinctive peaks of different ele­
ments found in the hydrogel, based on their binding energy. Fig. 5.C
3.4. Interactions and mechanism
displays the whole scan of the hydrogel, whereas Fig. 5.(D–H) depicts
the deconvoluted spectra of the C 1s, S 2p, N 1s, Na 1s and O 1s curves,
The concept behind the development of the LP-Ch hydrogels is to
respectively. The spectra observed at 281.6 eV was assigned to the
merge the chemical adsorption capability of lemon peel and chitosan,
presence of C–C, C– –C, and C–H bonds. The additional deconvoluted
along with the ability of the hydrogel composite to trap small molecules
peaks observed at the binding energies of 282.9 eV, 284.3 eV, and 285.9
within its porous structure. To effectively utilize this principle, the
eV was recognized as C–S, C–O, and O-C=O bonds. Two peaks were
polymer and particles must have minimal interaction, hence avoiding
observed at 165 and 165.6 eV in the S 2p spectrum, which can be
any interference with their mutual adsorption capacity. The LP-Ch
attributed to the C-S=O and sulphate group, respectively. The N 1s
hydrogel composite was found to show sufficient potential for the
spectra in Fig. 5.F shows distinct peaks corresponding to amine (396.8
removal of multiple cationic dyes. The positive charge of nitrogen (N)

Fig. 6. Effect of time (A), pH (B), adsorbent dosage (C) and initial concentration of dyes (D) on the removal of dye molecules by LP-Ch hydrogel.

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

atoms in dye molecules interacts with the negative charge of bromine 3.5.5. Optimization of temperature
(Br) atoms in CTAB, sulphur (S) atoms in AMPS, and carboxylate (COO-) The dye removal efficacy of the hydrogel was investigated at tem­
groups of the monomer due to electrostatic interactions. The removal of peratures of 20 ◦ C, 30 ◦ C, 40 ◦ C, and 50 ◦ C. Under the preoptimized
dyes is also facilitated by the dipole-dipole interaction and hydrogen condition, the highest % dye removal observed was 99.41 %, 99.25 %,
bonding.[51] 97.48 %, 95.10 %, 97.11 %, and 98.258 % for SO, MB, BF, TB, BG, and
CV correspondingly at a temperature of 50 ◦ C. At a temperature of 50 ◦ C,
the adsorbent and adsorbate had adequate interactions, leading to the
3.5. Optimization of multiple dye adsorption parameters by LP-Ch maximum percentage of dye removal. The removal capacity had a
hydrogel modest increase when the temperature was raised from 30 ◦ C to 50 ◦ C.
The removal efficiency of the dye was reduced when the temperature
3.5.1. Optimization of contact time exceeded 50 ◦ C. As the temperature rose, the strength of the electrostatic
The adsorption of all the dyes on LP-Ch hydrogel was observed for a interactions between the adsorbent and adsorbate molecules reduced,
contact time of about 0.5 h to 5 h of 10 mg L− 1 [Fig. 6(A)]. The values resulting in a drop in dye removal efficiency. The temperature rise
expanded as the contact duration increased, as indicative of the abun­ negatively affected the percentage of dye removal because it caused the
dance of unoccupied places on the hydrogel. The optimal duration of polymeric network to relax extensively, facilitating the release of
contact was determined to be 2.5 h for SO, BF, TB, and CV, 1.5 h for MB cationic dyes.[54]
and 2 h for BG. The adsorption process for each dye exhibited rapid
initial uptake on the polymeric surface, followed by penetration into the 3.6. Adsorption kinetics
hydrogel composite, leading to a progressive increase in adsorption
capacity over time. However, once the optimal time interval had Fig. 7. depicts the process of the cationic dyes getting absorbed into
elapsed, all of the available sites became fully occupied and reached a the LP-Ch hydrogel. Table 1 summarizes the kinetic parameters acquired
state of saturation at the adsorption equilibrium. from the plots. The correlation coefficient (R2) values demonstrated that
the pseudo-second-order model was the best fit for all the dyes. The
3.5.2. Optimization of pH pseudo-first-order model suggests that the rate of particle adsorption
The swelling behaviour of the hydrogel is significantly affected by onto the adsorbent is limited by physical adsorption. The pseudo-
the pH of the medium, resulting in a corresponding variation in the second-order model suggests that chemical sorption occurs on the sur­
elimination potential. The pH of the dye solution was adjusted within face through an exchange or sharing of electrons between the absorbent
the range of 2.0–12.0. Fig. 6(B) illustrated the pH-dependent dye and adsorbate. This process leads to a decrease in the total free energy of
removal characteristics of the LP-Ch hydrogel in the presence of multiple the system, allowing dye molecules to quickly diffuse into the core of the
cationic dyes. Under conditions of low pH level, cationic dye molecules hydrogel network. Intra-particle diffusion modeling refers to the
and H+ ions competed for adsorption onto the negatively charged assessment of how diffusion resistance might affect the process of
anionic sites of the hydrogel, resulting in a lower percentage of dye adsorption.[55]
removal. As the pH level ascended to 10.0, the dye % removal signifi­
cantly rose because the level of H+ ions dropped and OH- ions increased. 3.7. Adsorption isotherms
The highest efficacy of removal was observed at pH levels of 6.0, 8.0,
and 10.0 for MB, BG; TB, CV; and SO, BF respectively. The removal ef­ To determine the mechanism for adsorption on the LP-Ch hydrogel,
ficiency exhibited a gradual decline above a pH level of 10.0. This Langmuir, Freundlich, and Temkin adsorption isotherms were studied
phenomenon can be attributed to the repulsion between anions, spe­ (Fig. 8., Table 2). The Langmuir model showed an RL value range of
cifically the negatively charged OH– ions and negatively charged func­ 0.29–0.04 in the isotherm experiment, which falls within the 0.0 to 1.0
tional groups present in the hydrogel.[52] range indicating that the adsorption of dyes on the hydrogel composite
was efficient. The Freundlich model has the maximum correlation co­
3.5.3. Optimization of adsorbent dosage efficient for all the dyes, indicating its close fit with the experimental
The highest % removal of dyes was obtained through variation in the findings. It indicates that adsorption occurs by chemisorption. The
amount of adsorbent applied, ranging from 10 mg to 50 mg while Langmuir adsorption isotherm posits that the adsorbent develops a
keeping the contact duration and initial dye concentrations at their pre- single layer on the surface, while the Freundlich adsorption isotherm
optimized levels. The optimum quantity of adsorbent was estimated to illustrates the formation of multiple layers of the adsorbent on the
be 10 mg per 25 mL of a 10 mg L− 1 dye solution. This resulted in the polymorphous sites. The Temkin model predicts that the heat of
elimination of 97.13 %, 98.1 %, 96.44 %, 92.38 %, 96.78 %, and 96.48 adsorption exhibits a linear reduction as the adsorption amount rises.
% of SO, MB, BF, TB, BG, and CV, respectively [Fig. 6(C)]. The removal [56] (See Table 3.)
of dye was observed to be positively correlated with the increase in
adsorbent dosage due to the presence of a greater number of unoccupied 3.8. Thermodynamics
sites on the adsorbent.[53]
The change in entropy (ΔS) and the change in enthalpy (ΔH) were
3.5.4. Optimization of initial dye concentration estimated by assessing the intercept and slope of the linear graph of lnKd
Fig. 6(D) showed the % dye removal for the cationic dyes as the vs T. These values are listed in supplementary table S 07. The positive
initial dye concentration varies from 10 to 100 mg L− 1. The maximum value of ΔH suggests that the adsorption by LP-Ch hydrogel is endo­
amount of dye removal was obtained when the initial dye concentration thermic. The negative value of Gibbs free energy and the positive value
was 10 mg L− 1 for all the dyes, during the pre-optimized time for each of entropy indicate that the adsorption process is both feasible and
dye. The rise in initial dye concentration led to a higher driving force, spontaneous. Furthermore, the correlation between decreasing Gibbs
causing the available dye molecules to fill the unoccupied spots on the free energy and temperature suggests that adsorption becomes viable at
adsorbent until equilibrium was reached. The efficiency of removal elevated temperatures.[57]
reduced substantially as the concentration of dye increased. After
reaching a state of adsorption equilibrium, an increase in the initial dye 3.9. Recycling
concentration led to a reduction in the % dye removal. This can be
attributed to the lack of unoccupied sites on the hydrogel, rendering The work reveals the stupendous regeneration property of the LP-Ch
them unavailable for further adsorption.[52]. hydrogel, making it appropriate for the recycling of the hydrogel after

9
T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

Fig. 7. Pseudo-first order (A), Pseudo-second-order (B), and Intra particle diffusion (C) kinetic model for removal of dyes using LP-Ch hydrogel.

Table 1
Kinetic parameters for cationic dye adsorption by the hydrogel.
Model Pseudo-First order Pseudo-Second order Intra Particle Diffusion
− 1 − 1 2 − 1 − 1 2 1 1/2
Dyes qcal (mg g ) k1 (min ) R qexp (mg g ) qcal (mg g ) R kdif (g mg− min− ) C (mg g− 1) R2

SO 11.032 0.017 0.955 24.984 24.814 0.998 0.370 18.656 0.694

MB 9.051 0.044 0.731 24.788 23.810 0.994 0.123 22.506 0.186
BF 4.713 0.022 0.821 24.862 24.450 0.999 0.088 23.170 0.452
TB 12.024 0.030 0.918 23.483 23.641 1.000 0.227 19.903 0.710
BG 2.450 0.010 0.911 24.409 23.529 0.999 0.062 22.773 0.212
CV 5.608 0.017 0.788 24.726 23.585 0.996 0.103 22.283 0.239

Fig. 8. Langmuir (A), Freundlich (B), and Temkin (C) isotherm model for LP-Ch hydrogel.

Table 2
Adsorption isotherm parameters for cationic dye adsorption by hydrogel.
Model Langmuir Freundlich Temkin

Dyes KL (L mg− 1) Qmax (mg g− 1) R2 n KF (mg g− 1) (L mg− 1) 1/n R2 A (L mg− 1) B R2

SO 0.226 322.581 0.904 0.563 59.525 0.995 3.682 0.044 0.902

MB 0.231 370.370 0.826 0.544 68.786 0.991 4.356 0.042 0.869
BF 0.235 277.778 0.848 0.568 57.770 0.978 4.296 0.047 0.838
TB 0.048 588.235 0.887 0.685 28.761 0.989 1.101 0.030 0.933
BG 0.084 769.231 0.694 0.565 58.803 0.987 2.428 0.029 0.917
CV 0.080 769.231 0.874 0.573 55.731 0.990 2.188 0.028 0.947

adsorption from wastewater. The hydrogel showed reusability for up to 4. Conclusion

six cycles of adsorption–desorption–adsorption for all the dyes,
achieving an efficiency of over 90 % for SO, MB, BG and BF; and over 80 The CTAB-treated lemon peel-based hydrogel was developed. Chi­
% for TB, and CV. (Fig. 9.) Subsequently, the capacity of the hydrogel to tosan was also incorporated into the hydrogel to enhance the adsorption
remove dyes, reduced progressively as the binding sites became un­ efficacy for the elimination of multiple cationic dyes from the aqueous
available and the adsorbent matrices denatured. Therefore, this hydro­ solution. Hydrogels were synthesized using only lemon peel and only
gel has the potential to be an effective adsorbent with a high capacity for chitosan as well to compare. The swelling capacity of the RSM-CCD
recycling, while maintaining its fundamental structure up to certain optimized LP-Ch hydrogel was 39,028.6 %. This synthesized hydrogel
cycles. was characterized by FT-IR, TGA, BET, SEM-EDS, XRD, XPS and Zeta

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T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

Table 3
Comparative studies of various fruit peel-based hydrogels with their adsorption
capacities for dyes.
Dyes Time pH Adsorption References
Adsorbents (hr) capacity
(mg g− 1) /
% Removal

Orange peel-PAA Methylene 0.167 7 84 % [58]

hydrogel blue
Orange peel (OP)/ Methyl 24 7 26 and 10 [59]
N-vinyl-2- orange and and (mg g− 1)
pyrrolidone Congo red 6
hydrogel
Pineapple peel Methylene 0.33 8 101.94 (mg [60]
cellulose/ blue g− 1)
magnetic
diatomite
hydrogels
Chitosan/cellulose Methylene 1.67 – 32.05 (mg [61]
nanofiber blue g− 1)
isolated from
durian peel
waste/graphene Fig. 9. Regeneration and reusability efficiency of LP-Ch hydrogel.
oxide
nanocomposite Funding
hydrogels
Pineapple peel Congo red 2.5 4 75.19 (mg [62]
hydrogel g− 1) Triparna Das {3570 (UGC NET JULY 2018)} is thankful to University
Orange peel-based Congo red 48 8 12 (mg g− 1) [63] Grant Commission (UGC) India for financial support. This work was
hydrogel financially supported by the Council of Scientific and Industrial
Alginate/ Safranin O 0.33 10 85 % [64] Research (CSIR), India also.
Pomegranate
Peels hydrogel
beads CRediT authorship contribution statement
Hydrogel based on Methylene 1 10 18.53 (mg [65]
lemon peel and blue g− 1) Triparna Das: Writing – review & editing, Writing – original draft,
its isolated
Software, Project administration, Methodology, Formal analysis, Data
microcrystalline
cellulose curation, Conceptualization. Devendra K. Patel: Writing – review &
Lemon peel Basic 3 11 1.5133, [66] editing, Supervision, Resources, Project administration, Funding
adsorbent Fuchsine and 1.8142 (mg acquisition, Conceptualization.
and Eosin 3 g− 1) for BF,
and 1.2393,
1.5974 (mg
Declaration of competing interest
g− 1) for
Eosin There are no conflicts to declare.
Lemon peel as Reactive 1 2 95.12 % [67]
activated carbon Blue 49 Dye
Data availability
adsorbent
Mandarin (Citrus Safranin O 2 7 84.75 % [68]
reticulata) peel All data generated or analysed during this study are included in this
adsorbent published article (and its supplementary information files).
Lemon Peel- Safranin O, 2–2.5 6–10 99.93 %, Present
Chitosan Methylene 99.15 %, study
hydrogel blue, Basic 99.45 %, Acknowledgments
fuchsin, 93.93 %,
Toluidine 97.63 % and The authors appreciate the Director, CSIR-Indian Institute of Toxi­
blue, 98.90 % cology Research, Lucknow, India, for support. The authors are thankful
Brilliant
to Dr. Satyakam Patnaik for ATR-FTIR, TGA, and BET facilities. We are
green and
Crystal grateful for Mr. Joel Saji's assistance throughout performing character­
violet ization techniques for the research. Dr. Alok Pandey provided SEM-EDX
and DLS facilities, which we acknowledge. Many thanks to Dr. Natesan
Manickam for Multimode reader facilities. We want to thank Mr. Sau­
potential. The hydrogel exhibited % removal of 99.93 %, 99.15 %,
rabh Singh for his help with absorbance measurements in multimode
99.45 %, 93.93 %, 97.63 % and 98.90 % for SO, MB, BF, TB, BG and CV
plate reader. We are thankful to Alok Kumar Yadav from CSIR-IICT,
respectively. Kinetic studies have shown that the elimination of dyes
Hyderabad for XPS facilities, Dr. GNV Satyanarayana for his help, and
may be precisely defined by pseudo-second-order kinetics and Freund­
also to Dr. Kumer Sourav Keshri for his help in data analysis. For XRD
lich adsorption isotherm fitted well for the removal of dyes. The ther­
facilities, we want to thank Institution of Excellence, Vijnana Bhavana,
modynamic feasibility of adsorption for the removal of various dyes
University of Mysore. Our thanks to Mr. Kaushik Gautam, Department of
were assessed. The recycling study of the hydrogel demonstrated
Geology, Banaras Hindu University, for TGA facilities. The CSIR IITR's
exceptional regenerative capabilities. These adsorbents, which are both
manuscript number is IITR/SEC/MS/2024/08.
biodegradable and recyclable, can be utilized in textile factories for
water treatment. However, there are a few limitations, like fluctuations
Ethics approval and consent to participate
in pH levels in the wastewater might result in minor discrepancies in the
effectiveness of the hydrogels.
Not applicable. The study does not report on or involve the use of any

11
T. Das and D.K. Patel International Journal of Biological Macromolecules 275 (2024) 133561

animal or human data or tissue. 205063.2018.1489023 29 (2018) 1745–1763. doi:https://doi.org/10.1080/09

205063.2018.1489023.
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