Chemical Data Collections 38 (2022) 100834

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Data Article

Adsorption of a cationic dye (Methylene bleu) by Typha Latifolia:

Equilibrium, kinetic, thermodynamic and DFT calculations
Abdelhay El Amri a, Jaouad Bensalah a, *, Abdennacer Idrissi a, Kadiri Lamya a,
Abdelkarim Ouass a, Said Bouzakraoui a, Abdelkader Zarrouk b, El Housseine Rifi a,
Ahmed Lebkiri a
a
Laboratory of Advanced Materials and Proceeding Engineering (LAMPE), Department of Chemistry, Faculty of Sciences, Ibn Tofail University, B.P.
133, 14000 Kenitra, Morocco
b
Laboratory of Materials, Nanotechnology and Environment, Faculty of Sciences, Mohammed V University in Rabat, Av. Ibn Battouta, P.O. Box.
1014 Agdal-Rabat, Morocco

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

Keywords: In this work, the adsorption performance of methylene blue (MB) on rough R and Typha Latifolia
Methylene blue (MB) RS was studied. On one hand, the effect of various parameters on the adsorption efficiency were
Typha Latifolia studied knowing that the mass of the material, the adsorption time, the initial concentration and
FTIR/SEM/EDX
the pH of solution. All these different parameters influence the absorption capacity. The
Kinetic adsorption
maximum amount of adsorption of the different materials studied are estimated at 21.01 mg g− 1
density functional theory (DFT)
and 54.73 mg g− 1 at pH = 5. Under all optimal conditions, the relevant MB removal rates at R and
RS were 69.62% and 91.09%, respectively. On the other hand, the mathematical modeling
studied has shown that the S-type adsorption process and that the pseudo second order and
Langmuir are the most suitable models to describe the adsorption of the cationic dye via R and RS.
In fact, the study of Langmuir and Freundlich parameters has indicated that the removal of MB by
R and RS is favorable. Moreover, Theoretical calculations were carried out using simulations of
the (DFT) explored the interaction between the most reactive sites concerning the major bio­
sorbent constituent Typha Latifolia which is the cellulosic polymer and the cationic dye MB. The
comparative study of all experimental and theoretical results has confirmed the biosorption po­
tential of the studied biosorbent for the removal of dyes.

Specifications Table

Subject area Adsorbent, Cationic dye methylene bleu, Kinetic study

reed fiber, effect of adsorbent mass, Temperature effect, contact time and desorption study.
Compounds Typha Latifolia.
Data category Infrared spectra, MEB, EDX, UV–Vis spectra.
Data acquisition Evolution of pH and adsorption capacity, Variation of the percentage of elimination of MB, Evolution of the adsorption capacity of methylene bleu
format Safranin, Pseudo-second order kinetic model of the adsorption of MB and kinetic model.
(continued on next page)

* Corresponding author.
E-mail address: [email protected] (J. Bensalah).

https://doi.org/10.1016/j.cdc.2022.100834
Received 1 November 2021; Received in revised form 10 January 2022; Accepted 15 January 2022
Available online 17 January 2022
2405-8300/© 2022 Elsevier B.V. All rights reserved.
A.E. Amri et al. Chemical Data Collections 38 (2022) 100834

(continued )
Data type Evaluation of the MB retention capacity on Typha Latifolia, Parameters of the pseudo-first-order and pseudo-second-order kinetic model and
Thermodynamic Parameters.
Procedure This paper focuses on developing an effective and eco-frindly available adsorbent for the cationic dye Methylene bleu (MB).

1. Rationale

The cationic (MB) dye is one of the most commonly used textile dyes on silk, cotton, wood and other substrates such as paper. It can
be used for redox coloration, histological staining, and antiseptic in the treatment of superficial wounds. MB dye can cause many health
problems such as eye burns for humans or animals [1], respiratory problems, nausea, vomiting, sweating and cold sweat. Therefore, it
is necessary to remove this dye from wastewater. There are many methods to remove organic dyes from wastewater, including bio­
logical, chemical and physical methods [2]. However, these techniques are limited by its cost, its energy consumption and the pro­
duction of a large amount of sludge or toxic derivatives [3].
Biosorption was demonstrated to be efficient in elimination dyes and also differents metals from contaminated by using different
plant species. It is a cost-effective, efficient and friendly-environmentally method.
Typha Latifolia or reed fibers are a cosmopolitan plant, which can allows reliable aerobic treatment. Last decades, numerous re­
searches in recent years have enabled the development of this natural material in different fields such as a construction material
additive [4], bioenergy production [5], phytoremediation of heavy metals [6], etc. In fact, reed fibers are an abundant substance that
currently represents nearly 15% of the station fleet [7].
In this context, the current study has investigated the adsorption efficiency of two materials R and RS prepared based on Typha
Latifolia for methylene blue (MB) dye from contaminated solutions. Initially, the parametric study has been realized through several
parameters. Also the thermodynamic parameters have been calculated using Vant’Hoff curves. Numerous kinetic models and
adsorption isotherms have been tested to describe the adsorption mechanism. DFT calculations were applied to understand the
adsorption process of the methylene blue dye onto R and RS.

2. Procedure

2.1. Material

The studied reed fibers were collected from Oued sabou located in Kenitra city, Morocco during September. They were washed by
distilled water to eliminate all impurities and were dried in air for 48 hours. The obtained materials were ground by an electric grinder
and then were carried out with an electric sifter in order to obtain the same particle size. In this study, the size of 250 μm was used to
study all parameters, the obtained power R.

2.2. Preparation of solutions

The studied is the cationic MB dye (IUPAC) named 3,7-bis (dimethylaminophenothiazine-5-ammonium chloride). This dye is
characterized by a purity of 95 % FLUKA ™, a chemical formula C16H18N3SCl, and a molecular weight of 373.90 g.mol− 1. The chemical
formula of methylene bleu is shown in Table 1.
The stock solutions were prepared by dissolving 1 g of methylene blue in 1 L of distilled water. All solutions concentrations were
measured through the UV / VIS spectrophotometer at a wavelength of 665 nm.
For this dye, a similar study on the influence of the different parameters (contact time, m/v ratio and pH) was carried out. A mixture
of 100 mL of MB at a concentration of 10 mg/L and 0.1 g of support at 3 pH 8 is kept under magnetic stirring at room temperature for
various time intervals. Displays an optimal shaking time of 3 hours. For longer times, a gradual increase in the extraction efficiency is
observed.

Table 1
Chemical characteristics of MB.

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2.3. Chemical analysis of the adsorbent

The quantity of three lignocellulosic components (cellulose, hemicellulose and lignin) in the filter planted reeds was determined by
the method proposed by Yang et al. (2006). In the experimental process, 4 kinds of a chemical will be used; (1) Acetone, (2) Sodium
hydroxide (Na Oh - 0.5 mmol/L), (3) Sulfuric acid (98%).

2.3.1. Extraction analysis

The prepared adsorbent is treated with a mixture of toluene and ethanol at constant temperature for 3 hours. The remaining residue
is dried in order to obtain constant weight at 105–110 ◦ C. The adsorbent is stocked in a desiccator. The weight of the extract is
calculated as follows [2].
To determine the amount of extracts in the biomass solvent extraction (60 mL of acetone per 1 sample of dried biomass) was used
and the temperature was kept at 90 ◦ C for 3 h. After that, the sample was dried in an oven (105–110 ◦ C) until a constant weight was
obtained. The difference in weight before and after extraction is the amount of extracts.
m0 − m1 = amount of extract (g) (1)

2.3.2. Hemicellulose analysis

The obtained extract m1 was put into a round bottomed flask, 150 mL NaOH solution 20 g L− 1 was added, refluxed for 3.5 hours and
then Filtered. In addition, it was washed the material and dried to constant weight. It is then placed in a desiccator. The weight of
hemicellulose is calculated as follows:
To determine the amount of hemicellulose, 150 mL of sodium hydroxide (NaOH) solution 20 g L− 1 and the temperature was kept at
80 ◦ C for 3.5 h. After that, the sample was washed with distilled water until no more Na + was detected (indicated by the pH value of
the approaching solution, then it was dried until at a constant weight The difference between the weight of the sample before and after
this treatment is the hemicellulose content calculated as follows:
m1 − m2 = hemicellulose content (g) (2)

2.3.3. Lignin analysis

The extracted residue was put into a round bottomed flask, 30 mL H2SO4 was added and the mixture was preserved at 14 ◦ C for 24
hours. After 24 hours, the solution was diluted with 300 mL distilled water and was heated for 1 hour. The obtained mixture was
filtered and was rinsed until the disappearance of sulfate ions [5]. The residue is finally dried in an oven, cooled in a dryer and weighed
per m3, the weight of lignin is calculated by the following equation:
To determine the amount of lignin, 30 mL of 98% sulfuric acid was added for each gram of sample (biomass dried without
extraction). After the sample was kept at room temperature for 24 h, it was boiled at 100 ◦ C for 1 h. mixture was filtered, then the
residue was washed until the sulfate ion in the filtrate was undetectable; it was then dried to constant weight. The weight of the residue
is recorded as the lignin content. Finally, the cellulose content is calculated by difference, assuming that extracts, hemicellulose, lignin
and cellulose, are the only components of all biomass calculated as follows:
m2 − m3 = lignin content (g) (3)

2.3.4. Cellulose analysis

The cellulose content was determined by calculating the difference between the adsorbent weight before and after extraction using
the obtained results corresponding to the other components [6].
(m0 − m1 ) + (m1 − m2 ) + m3 + m4 = 1g (4)

2.3.5. Humidity
The percentage of humidity was determined through comparing the adsorbent weight before m1 and after m1 drying in an oven at
110 ◦ C during 48 hours. This parameter can be calculated by the following formula:
m1 − m2
H (%) = (5)
m1

2.4. Treatment of the adsorbent

Typha Latifolia was chemically treated to activate functional groups. The activated adsorbent was dried and was used for
adsorption study [7]. Soda treatment involves mixing an amount of reed fibers with 0.1 M of sodium hydroxide to obtain a
weight/volume ratio of 1/5. Before washing through distilled water until to obtain a neutral powder. The adsorbent was dried at
105 ◦ C, was ground, was sieved in order to recover particles less than 0.315 mm and then was named RS [8].

2.5. The point of zero charge (pHpzc)

The point of zero charge is an important parameter is very important for the adsorption phenomena, especially when electrostatic

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Table 2
Extraction analysis of reed fibers.
Composants weight (%)

Extractives 12.00
Hemicellulose 26.00
Lignin 23.00
Cellulose 39.00
Humidity 13.42

force is involved in the mechanism. In order to determine the pHpzc value, 50 mL distilled water was put into a flask. The pH was
adjusted by adding NaOH or HCl solution. Then 50 mg of material sample was added to each flask. The suspension should be stirred at
room temperature for 24 hours before the final pH is determined. Refer to the figure pHf = f (pHi), where the isoelectric point is the
intersection of the obtained curve and the line pHi = pHf.

2.6. Kinetic study

The removal experiments of methylene blue dye from aqueous solutions by reed fiber were investigated through batch method. The
studied adsorbents R and RS were added to several conical flasks containing 200 mL of MB solutions. The solution pH was adjusted by
adding HNO3 or NaOH. The concentration of methylene blue solution before and after biosorption was determined by UV–Vis
spectrophotometer. The biosorption capacity (mg g− 1) of methylene blue on reed fibers was calculated by the following formula:
V
Qe = (Ci − Ce) ∗ (6)
m
To determine the dye removal rate, the following equation was used:
(Ci − Cf )
R% = ∗ 100 (7)
Ci
With C0 and Ce are the initial and evenness concentrations, respectively, is the mass of biosorbent and V is the volume (mL) of
solute.
In this paper, the nonlinear fitting method is used to fit the dynamic and equilibrium models by using Origin 8.0 software [10].

2.7. Theoretical research DFT

The quantum chemical various parameters, which were reported of this paper, were determined by Gaussian method. The DFT
method used included a B3LYP hybridization function based on 6–31 G for the geometric optimization of molecular structures of MB
and cellulose and their oxidation (glucuronic acid formation) [9]. In addition, Some quantum chemical various parameters of the
optimized structure were calculated, such as the highest occupied structural orbital energy (EHOMO), the lowest unoccupied structural
orbital energy (ELUMO), energy gap (ΔEgap), dipole moment (μ), total hardness (η), The absolute electronegativity (χ) were calculated
by the following formula:
ΔEGAP = ELUMO − EHOMO (8)

ELUMO − EHOMO
η= (9)
2

1
σ= (10)
η

− (EHOMO + ELUMO )
χ= (11)
2

3. Data, value and validation

3.1. Characteristic research

The main components of the studied adsorbent were hemicellulose. Lignin and cellulose form secondary components. The analysis
results are seeing in Table 2.
The fraction of cellulose, hemicellulose and lignin in the filters of sugar cane were analyzed as a function of weight loss. Extracts are
basically chemical components that contain oils, fatty acids, fatty alcohols, phenols, terpenes, steroids, resin acid, resin, waxes and
other biological compounds. As a result, the leaves give usually higher yields in comparison with the stem and the root. These extracts
are concerned for the color, the smell and the strength of biomass. It is mainly composed by (39%) cellulose and (26%) hemicellulose.
Moreover, the lignin ratio is determined through the difference between the holocellulose and cellulose reaching a yield of 23 %.

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Fig. 1. pHpzc corresponding to R and RS.

Fig. 2. Spectra (FTIR) of (R) (a) and (RS) (b).

Extractable materials were also found with a ratio of 12 %.

3.2. Determination of pHpzc

According to (Fig. 1), the pHpzc values of rough and treated reed fibers are 5.08 and 6.58 respectively. In fact, upper this value the
adsorbent surface has a positive charge and below this point, the surface has a negative charge, which can provide an efficient bio­
sorption of methylene blue, cationic dyes, alkali and hydroxyl in this interval [8]. On one hand, positive charge of RS and R, are at pH 〈
pHpzc can be explained by protonation of functional groups. On the other hand, the negative charge of the studied adsorbents at pH 〉
pHpzc is due to deprotonation of functional groups of R and RS surfaces and formation of O− − ions [6].

3.3. Fourier-transform infrared spectroscopy (FTIR)

The dye adsorption on an adsorbent surface involves the participation of carboxyl, amino, hydroxyl and other functional groups.
Sodium hydroxide involves carboxyl groups in the cell surface of reef fibers [13]. It can be seen from the peaks at 1230 cm− 1, 1366
cm− 1, 1734 cm− 1 and 3332 cm− 1 (Fig. 2). Treatment process increased the adsorption capacity of MB by 23%, indicating that carboxyl

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A.E. Amri et al. Chemical Data Collections 38 (2022) 100834

Fig. 3. FTIR spectra of R and RS before (a,b) and after adsorption (c,b).

Fig. 4. EDX of rough resin (A) and modified resin (B).

group participated in the adsorption process [14].

The infrared spectra of rough and treated reed fibers were analyzed. The characteristic vibration band was interpreted based on the
literature [15]. Both of the infrared curves has shown a band at 3335 cm− 1 corresponding to the OH bond stretching vibration of

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Fig. 5. Micrographs corresponding to (R) (A) and (RS) (B) before BM adsorption. Micrographs corresponding to (R) (C) and (RS) (D) after
BM adsorption.

phenol and lignin groups, and the aromatic and aliphatic structures of cellulose. The visible peak at 2890 cm− 1 corresponds to the
asymmetric elongation vibration of cellulose CH bond [16]. Fig. 3 see the FTIR spectra of two adsorbent (R and RS) before and after
adsorption.
The band at 3335 cm− 1 is related to the elongation of OH groups. The C-H elongation at 2890 cm− 1 attributed to the presence of
cellulose. It is clear that the treated sample contains more -OH groups than the untreated sample. The band at 2350 cm− 1 is related to
the - OH of absorbed water, and the typical cellulose band at 1030 cm− 1 is due of the C-O-C elongation of b-glycoside bond. The
appearance of these peaks indicates that the proportion of cellulose content increases after the removal of non-cellulose materials by
chemical treatment [15].
The peak of R at 1740 cm− 1 is attributed to the C = O voltage of acetyl polysaccharide and uronic ester group, which is also related
to the p-coumarin acid of lignin and / or hemicellulose. After chemical treatment, the absence of this peak indicates that most of the
lignin and hemicellulose come from microfibers. Moreover, the peak intensity decreased significantly at about 1236 cm− 1, which is
related to the COO vibration, elongation of acetyl group in hemicellulose and C-O of aryl group in lignin. The significant peak at 1429
cm− 1 is related to the presence of CH2 at 1370 cm− 1. The absorbance at 1316 cm− 1 is caused by the fluctuation of CC axis and CO [17].
The vibration of C-O-C pyranose ring skeleton occurred at 1054 cm− 1 and 1031 cm− 1 [18].
The results Fig. 3 shown, the biosorbent capacity depended mainly on the wall properties of the bioadsorbent studied. Adsorption
can occur by complexation of MB with surface functional groups such as C-H, C = O, O-H, C-O, O-C-O and -COO-. The difference in MB
biosorption can be attributed to the different functional groups of the broad-leaved cattail cell bioadsorbent.

3.4. SEM and EDX analysis

As shown in (Fig. 4), they micrograph of the treated sample (enlarged to 250 times) shows that the longitudinal tracheid rearrange
into a uniform ladder like structure, which is only the effect of acidic hydrolysis of the material. The porous structure on the surface is
obvious, which indicates that hemicellulose can be degraded and that extractable materials can be removed after chemical

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Fig. 6. Effect of stirring time on the dye concentration (a) and solution pH (b), [MB] = 10 ppm; m = 0.1 g ; V = 100 mL; pHi = 5 ; t= 3 h.

Fig. 7. Effect of the adsorbent mass on the adsorption process, [MB] = 10 ppm; V = 100 mL; pHi = 5 ; T= 298 K ; t= 3 h.

modification. As shown in (Fig. 4A) and (Fig. 4B), the hidden pores are also exposed in the longitudinal cavity wall. Removal of
hemicellulose is considered to have the effect of increasing pore volume [19].
The morphology and structure of the reed fiber before and after adsorption process were realized by SEM technic. Therefore, the
external and lateral EDX images show the surface morphology of the biomass, (Fig. 5C) and (Fig. 5D). The main results showed that
biomass had dense lingo cellulosic structure, as shown in (Fig. 6A) and (Fig. 6B) [20]. As shown in (Fig. 6D), methylene blue was not
clearly observed in biomass microspores. It has been observed that there are obvious differences in the phenomenon of biosorption.
Fig. 5 shows SEM images recorded from the raw R and modified RS surface region. From these images, it is possible to observe that
the morphology of the surface of our bioadsorbent varies depending on the activation used in our NaOH treatment process. The
bioadsorbent presents a very heterogeneous and irregular morphology where the aggregates are distributed over its entire surface.
These aggregates showed different sizes and irregular shapes. Although R exhibits an irregular surface morphology, no aggregate was
found (see Fig. 5B). In addition, the RS bioadsorbent shows a rough surface with interconnected vessels resulting in a "brain"
morphology. Deviations in the morphologies of these two resins can be caused by distinct interactions between the support and the MB
molecules (see Fig. 5D). In addition, the quantitative analyzes have shown that the amount of MB in RS is greater than that determined
in R.

3.5. Kinetic study

3.5.1. Effect of exposure time

In order to evaluate the effect of contact time on the adsorption of MB on RS and R surfaces, the adsorption experiments were
carried out in BM solution with optimal concentration (10 mg L− 1) and optimal pH value of 5 at 25 ◦ C for 5 at 180 minutes. All
experimental data are shown in (Fig. 6) and have indicated that the rendement adsorption of the studied MB onto coriander seeds
increases with the increase of time). The rough adsorbent R has reached the maximum value 69.37 % of adsorption rate after 90
minutes while the activated adsorbent RS has yielded a rate of 92.12 % during 50 minutes. At the first stage of adsorption, the

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A.E. Amri et al. Chemical Data Collections 38 (2022) 100834

Fig. 8. Effect of initial solution pH on the adsorption process [MB] = 10 ppm; V = 100 mL; T= 298 K, m= 0.1 g; t= 3 h.

adsorption rate has increased due to the existence of a large number of free adsorption sites on the RS surface. However, for the rough
adsorbent R, it is difficult to occupy the remaining external vacancies due to the repulsive force of MB structural on the solid surface
and in the water phase. Moreover, the achieved values of solution pH after extraction experiments corresponding to R and RS have
shown that the acidity of the studied aqueous phases decreased during the extraction process, which led to the consumption of H+ ions.
This result proves that there is competition amongst H+ ions and MB structural to be fixed on the adsorbents surfaces [22].

3.5.2. Effect of adsorbent mass

In order to determine the optimal mass of rough (R) and treated reed fiber (RS) which is sufficient to remove MB dye, several
experiments were carried out with masses ranging from 10 to 80 mg L− 1. The obtained results were illustrated in (Fig. 7) and have
shown that the adsorption rate of methylene blue increased with the increasing value of (R) and (RS) doses. This behavior is due to the
fact that the adsorption sites increase with the increase of the adsorbent mass of the adsorbent [21].

3.5.3. Effect of solution pH

The solution pH is an important factor affecting the adsorbent structure, the adsorbate and the adsorption mechanism. In fact, it
influences not only the surface charge but also the distribution and the morphology of dyes molecules. The effect of solution pH on the
adsorption rate of BM was studied with a pH value ranging from 3 to 8 which was adjusted using HNO3 or NaOH. All studied aqueous
solutions were recuperated after adsorption process and then were analyzed by UV Vis Spectrum. The obtained results were illustrated
in Fig. 8 and have shown that the adsorption competence of MB increases at 68.28 % to 94.09% at pH 3 at 5 for RS and from 44.13% to
69.43 % at pH 3–5 for R. In fact, at low pH value, the adsorbent surface will be surrounded by H+ ions, which reduce the interaction
and prevent the bond formation between MB molecules and adsorption sites through electrostatic repulsion and competition amongst
H+ ions and methylene bleu. In contrast, at high pH value, the concentration of H+ decreases results a good interaction amongst MB
ions and surface sites [23].

3.5.4. Effect of bm initial concentration

In order to study the effect of MB concentration on adsorption capacity, the study is carried out at multi concentrations ranging
from 10 to 80 mg g− 1. It can be seen that the adsorption capacity of MB by the two materials increases from 5 to 21 mg g− 1 with the
increase of initial dye concentration using R and from 8 to 54 mg g− 1 using RS. These results can be explained by the fact that at low
concentration value, the dye molecules can interact with the binding sites on the adsorbent surface, which promotes the adsorption
efficiency. Above the initial concentration 60 mg g− 1, the adsorption capacity become stable due to saturation of adsorption sites [11].

3.5.5. Effect of temperature

The effect of the temperature on the cationic dye MB adsorption by R and RS was investigated. Five temperature values 298, 308,
318, 328 and 338 K were considered (Fig. 10). The obtained results have shown that the eliminate rate of the cationic dye MB by R and
RS decreases from 90.84 to 57.06 % for RS, when the temperature changes 298 to 338 K, respectively while the adsorption rate
decreases from 67.98 to 44.48 % for R. This result can be explained by the fact that The MB adsorption of on rough and treated reed
fibers is exothermic in nature and that low temperature promotes the adsorption process [4]. However, overheating can disadvantage
the adsorption process and may lead to an increase in desorption kinetics [24,25].

3.6.5. Desorption study

When the surface concentration is greater than the adsorption capacity, desorption can be achieved. Therefore, the adsorption
capacity of reed fiber in acidic environment was studied. The following table shows the effect of pH value on the desorption capacity. It
is clear that desorption increases at low pH value. This result has shown that the desorption effect is the best when the high acid pH
value is 3 [26].

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Table 3
Desorption rate of MB from charged R and RS at different pH values.
pH Values Adsorbent pH=3.00 pH=4 .00 pH=6.00

Desorption rate (%) R 98.00 96.00 89.00

RS 99.00 98.00 94.00

Table 4
Comparative study of the adsorption of MB by different natural adsorbents.
Biosorbent Q (mg g− 1) References

Carica Papaya 32.25 [42]

Tunisian Phragmites australis 41.20 [43]
Modified Phragmites australis 46.80 [44]
Rough reed fibers (R) 21.01 The present study
Treated reed fibers (RS) 54.73 The present study
Coriandrum Sativum seeds 107.53 [45]

Table 5
Thermodynamic parameters corresponding to the adsorption process.
T(K) LnKd (L g− 1) ΔH* (kJ mol− 1) ΔS* (J mol− 1
K− 1) ΔG◦ (kJ mol− 1)

R 298 0.75 -2.14

308 0.65 -20.45 -61.41 -1.53
318 0.51 -0.92
328 0.13 -0.30
238 -0.22 0.30
RS 298 2.30 -5.40
308 1.46 -41.05 -119.61 -4.21
318 1.15 -3.01
328 0.60 -1.81
338 0.29 -0.62

The negative charge of R and RS surface and the free electron of nitrogen atom constituting dye molecule competitively bind the
hydrogen bond to acid medium, which confer the interaction between cationic dye and biomass (R and RS). Table 3 has shown clearly
that a decrease in pH increases the desorption rate, which becomes effective in highly acidic media [27].

3.7. Comparative study

As shown in Table 4, a large number of studies have been carried out natural adsorbents as a removal of methylene blue. It is found
that the adsorption capacity of reed fibers is among the highest adsorption capacities of mentioned adsorbents. All results are
encouraging for testing R and RS as a low-cost removal of methylene blue dye from industrial wastewaters.
Table 4 represented some similar studies that have investigated the methylene blue removal. It is clear that the studied reed fibers
in both of rough and treated forms modify induce a good adsorption efficiency compared to the raw and modified Phragntic austral is
or the Carica Papaya. All results are encouraging for the low cost eliminate of methylene blue dye from industrial wastewater.

3.8. Thermodynamic study

Thermodynamic parameters of the studied adsorption process were determined at different temperatures through the following
equations:
ΔG∘ = − RTln(Kd) (12)

ΔGads = ΔHads − TΔSads (13)

− 3 − 1 − 1
Where T is the temperature (K), R (8.314 × 10 kJ mol K ) is the ideal gas constant and Kd is the partition coefficient:
Qe
Kd =
Ce
ΔH* and ΔS* are determined by the slope and line intercept of ln Kd as a function of 1 / T, using the following van’t Hoff equation
[2]:
ΔS∗ ΔH∗
ln(Kd) = − (14)
R RT

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Table 6
Langmuir and Freundlich parameters.
isotherm parameters Adsorbents
R RS

Freundlich Kf (mg g¡1) 5.37 346.73

n 2.69 0.57
R2 0.888 0.781
Langmuir Qm (mg g− 1) 23.26 66.67
KL (L mg− 1) 0.153 1.72
R2 0.996 0.996

Table 7
Parameters of kinetic models.
Model Parameters Biosorbent
R RS

Pseudo-first order qe- calcul (mg g )

¡1
6.61 7.32
k1(min¡1) 0.01 0.02
R2 0.73 0.98
Pseudo-second order qe- calcul (mg g− 1) 32.79 49.84
k2(min− 1) 0.02 0.10
R2 0.77 0.9997

The obtained thermodynamic parameters are summarized in table 5. Based on these results, the free energy is negative for all
temperature values. This result indicates that the adsorption of MB on R and RS is spontaneous regardless of the temperature value
[28]. The free enthalpy is negative which confirms that the adsorption process is exothermic and that high temperature is not promoter
of the adsorption process. Moreover, the entropy value △S* is negative, which means that MB structure maintain the order in the
solid-solution interface during the adsorption process [29].

3.9. Adsorption isotherms

The application of biosorption isotherms is useful for describing the interaction between biosorbents and providing information
concerning the biosorption mechanism, surface properties and affinity of plant fibers. The obtained results from the study of the
temperature effect were used through Langmuir model by the following equation [12].
Ce 1 Ce
= + (15)
Qe Kl ∗ Qmax Qmax
Ce (mg L− 1) is the equilibrium concentration, Qe (mg g− 1) is the equilibrium adsorption capacity, Qm (mg g− 1) is the maximum
adsorption capacity, and KL (L mg− 1) is the Langmuir constant.
The obtained results from the study of the temperature effect were also used through Freundlich model by the following equation
1
LogQe = lnKF + logCe (16)
n
The graphical representation of the logarithm (Qe) of the Freundlich empirical constant as a function of logarithm (Ce) is a straight
line of 1 / N directional coefficient and logarithm (KF) coordinates.
According to Table 6, the correlation coefficients corresponding to Langmuir model for both of the adsorbents are equal to unity.
Also, the R and RS the biosorption obeys Langmuir model which assumes monolayer coverage of MB dye over the homogeneous
surface of RS [30], and the adsorption of each molecule onto the surface has the same adsorption activation energy [31,32].

3.10. Kinetic models of adsorption

The experimental data of MB adsorption on R and RS were investigated using pseudo first order and pseudo second-order kinetic
models. All corresponding parameters and correlation coefficients were listed in Table 6.
According to Table 7, we observe that the correlation coefficient R2 corresponding to the second-order kinetic model is equal to
unity. Moreover, the obtained values of adsorption capacity from the mathematical modeling study are similar to the experimental
ones. This observation suggests that the adsorption of MB by RS from aqueous solution followed the pseudo-second-order model [33].
To sum up, the adsorption process is a chemical adsorption type inducing the exchange of electrons between the adsorbent surface and
dye molecules.
This indicates that the theoretically calculated values are very close to those which are obtained experimentally. Indeed, according
to these results obtained, it turns out that the pseudo-second order kinetic model is verified which allowed us to conclude that the
nature of the adsorption exploited of the dye MB by the biomass RS.

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Table 8
Optimized structures, HOMO, LUMO and MAP.

4. Function theory (DFT) study

The effect of molecular structure on the adsorption process of MB on the adsorbent surface including cellulose and glucuronic acid
molecules was investigated using quantum chemical calculations based on the DFT theory. Table 8 shows the optimized molecular
structures, HOMO orbitals, LUMO orbitals, and MB orbitals of cellulose and glucuronic acid, as well as molecular electrostatic potential
maps. The HOMO and LUMO orbitals are extensively spread over the MB molecule as well as the oxygen atoms that make up cellulose
and glucuronic acid. All of the findings point to active adsorption sites being present in the compounds under investigation. The
molecule electrostatic potential (MEP) corroborated this result [34].
In reality, the molecular electrostatic potential is a simple model for understanding polarization locations and relative reactions.
The new distribution of molecules in three-dimensional space can be visualized using an electrostatic potential map. The MEP of MB,
cellulose, and glucuronic acid was computed using the DFT method in this context, and the results are shown in table 8 [35]. The
negative regions of MEP, the blue and yellow colors, which are found on the oxygen, nitrogen, and sulfur atoms, are the most
appropriate sites for electrophilic assaults, as seen in table 8. The values of EHOMO, ELUMO, EGAP, and for MB, Cellulose, and glucuronic
acid molecules are obtained to better understand the effect of MB adsorption on the structural characteristics of cellulose and

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Table 9
Quantum chemical parameters of MB, Cellulose, and Cellulose oxide, at DFT/B3LYP 6–31G(d,p).
Quantum chemical parameters BM cellulose Oxide cellulose

ETot(eV) -32,177.11 -35,304.04 -39,331.83

EHOMO(eV) -3.66 -7.20 -7.23
ELUMO(eV) -0.09 1.12 -0.78
ΔEGAP(eV) 3.58 8.32 6.45
μ (Debye) 2.56 1.08 4.72
η (eV) 1.79 4.16 3.22
χ (eV) 1.89 3.04 4.00

Fig. 9. Effect of initial MB concentration on the adsorption process, m = 0.1 g; V = 100 mL; pHi = 5; T= 298 K; t= 3 h.

Fig. 10. Effect of temperature on adsorption process, [MB] = 10 ppm; V = 100 mL; m= 0.1 g; t= 3 h; pHi = 5.

glucuronic acid. Table 9 summarizes the outcomes collected. In fact, the total energy value can be used to measure the reactivity and
stability of molecules; a high ETot value indicates great chemical stability and consequently a low affinity value for adsorption capacity
[36].
The ability to lose electrons is often related with the greatest occupied molecular orbital HOMO energy, whereas the ability to fix
electrons is generally connected with the lowest empty molecular orbital LUMO energy. As a result, these various factors are linked to
electron affinity [37]. A high EHOMO value indicates the electron transfer affinity for a suitable acceptor molecule and then promotes
the adsorption of methylene bleu molecules on the surface of cellulose and glucuronic acid. Furthermore, the molecule’s strong
reactivity is reflected in its low EGAP value, which facilitates the adsorption of cationic dye on the surfaces of cellulose and glucuronic
acid, indicating that the adsorption process is very durable.
The polarization of the molecule causes the dipole moment, which is related to the adsorption capacity. The adsorption between
MB molecules and the surface of the adsorbent comprising cellulose and glucuronic acid can be enhanced by a high value. As a result,
the large dipole moment created can cause electron transfer from the MB molecule to the cellulose and glucuronic acid surfaces [38].
Furthermore, depending on the adsorption model, the size and direction of the dipole moment vector when MB is adsorbed on the
surface of glucuronic acid varies. The overall hardness and softness measurements can also be used to determine the stability and

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Fig. 11. The Van ’t Hoff MB adsorption curve on R and RS..

Fig. 12. Linear form of the Langmuir and Freundlich models.

reactivity of the molecules being investigated. Total hardness refers to a molecule’s resistance to deformation or polarization in the
absence of chemical interactions. In reality, the determined values of the interacting molecules’ total hardness and overall softness can
aid their adsorption on a suitable surface [34].
Furthermore, Van Der Waals diffusion forces may play a role in the adsorption of MB molecules on R and RS surfaces, validating the
isoelectric point characterization results. Table 9 summarizes the computed values of the varied BM adsorption energies on the cel­
lulose and glucuronic acid surfaces. A negative adsorption energy value implies that the adsorption process is spontaneous, whereas a
high binding energy value suggests that the adsorption process is steady [39]

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Fig. 13. Pseudo first order (A) and pseudo second-order (B) models.

Fig. 14. Mechanisms ionic and electrostatic interaction.

5. Possible mechanisms of biosorption

The -OH groups found in the cellulose and hemicellulose of reed filters, as well as the aromatic structures contained in the lignin,
influence the biosorption process. The cationic characteristics of methylene blue, on the other hand, have been proven to delocalize the
charge. They can be found in sulfate or nitrogen; however, they are more commonly found on nitrogen atoms. Because carboxyl groups
are available for adsorption of the charged dye at these pH > pHPZC values, and the biosorbent surface is negatively charged due to the
COO− , the optimal pH range for biosorption with methylene blue was 5.0 to 8.0. As illustrated in Fig. 14, species produced from an
alkaline solution [40]. he existence of -OH functional groups in cellulose and hemicellulose in the fibers, as well as the presence of the
free electron doublet of nitrogen atoms present in the dye, may be seen in FTIR examination (Figs. 14,15). Sulfuric atoms were
demonstrated to have a similar process in (Figs. 14,15). The - dispersion interaction between the lignin rings and the methylene blue
rings is depicted in the third suggested mechanism. The described mechanism is separated into electrostatic interactions, hydrogen
bond formation, and electron donor-acceptor and π- π dispersion interactions, as shown in the last figure [41].

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Fig. 15. Possible adsorption Mechanisms of MB on reed fibers.

6. Conclusion

Typha Latifolia fibers were found to be an efficient removal of methylene blue dye from contaminated solutions reaching 21 and 54
mg g− 1 respectively for the rough and the treated adsorbent. In fact, the adsorption process was influenced by contact time, solution
pH, adsorbent mass, and temperature and dye concentration. The analysis of thermodynamic parameters values indicated the
exothermic, the stable and spontaneous nature of the dye adsorption process on the surface of R and RS. On the other hand, the kinetic
measurements have shown that the studied process follows the pseudo-second-order model. In addition, the adsorption process was
described by Langmuir model. Moreover, the theoretical study of chemical interactions between cellulose and oxidized cellulose that is
the major component of reed fibers and methylene blue dye. All the obtained findings were in a good correlation with spectroscopic,
experimental, mathematical modeling and thermodynamic studies. Finally, the present study revealed that this new adsorbent is low
cost, indigenous, available material and can be applied as a removal of MB dye contained in industrial effluents. The weight of the
residue is recorded as the lignin content.
Finally, the cellulose content is calculated by difference, assuming that extracts, hemicellulose, lignin and cellulose, are the only
components of all biomass calculated as follows. The latter was carried out by grafting carboxylic functions with an excellent yield. The
IR spectroscopic study confirms the presence of COOH grafts. The support thus prepared has a good ability to cleanse water laden with
coloring matter. Indeed, the study of the influence of the various parameters (time, mass, pH) made it possible to conclude that (MB) is

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rapidly adsorbent by the grafted fibers: 90 min with a yield of 69% for R and of 95% for RS as well as at basic and acidic pH. The
minimum ratio (mass of the support / volume of dye solution) corresponding to the maximum adsorption rate (95%) is 0.1 g (Figs. 9,
11, 12, and 13).

Declaration of Competing Interest

The authors declare that they have no known competitive funding or personal relationships that could have appeared to influence
the work reported in this article.

Acknowledgements

The authors thank the University Center for Analysis, Technology and Incubation Transfer Expertise (CUAE2TI), under the Ibn
Tofaïl University of Kenitra, and the National Center for Scientific and Technical Research CNRST of Morocco have made available to
the scientific equipment of the UATRS division.

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