polymers

Article
Adsorption Behavior of Methylene Blue Cationic Dye in
Aqueous Solution Using Polypyrrole-Polyethylenimine
Nano-Adsorbent
Abdullahi Haruna Birniwa 1,2 , Habibun Nabi Muhammad Ekramul Mahmud 2, * , Shehu Sa’ad Abdullahi 3 ,
Shehu Habibu 4 , Ahmad Hussaini Jagaba 5 , Mohamad Nasir Mohamad Ibrahim 6 , Akil Ahmad 7 ,
Mohammed B. Alshammari 7 , Tabassum Parveen 8 and Khalid Umar 6, *

1 Department of Chemistry, Sule Lamido University, Kafin-Hausa P.M.B 048, Nigeria

2 Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
3 Department of Polymer Technology, Hussaini Adamu Federal Polytechnic Kazaure,
Kazaure P.M.B 5004, Nigeria
4 Department of Chemistry, Faculty of Science, Federal University Dutse, Dutse P.M.B 7156, Nigeria
5 Department of Civil and Environmental Engineering, Universiti Teknologi Petronas,
Seri Iskandar 32610, Malaysia
6 Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia,
Gelugor 11800, Malaysia
7 Chemistry Department, College of Sciences and Humanities, Prince Sattam bin Abdulaziz University,
Al-Kharj 11942, Saudi Arabia
8 Department of Botany, Aligarh Muslim University, Aligarh 202002, India
Citation: Birniwa, A.H.; Mahmud, * Correspondence: ekramul@um.edu.my (H.N.M.E.M.); khalidumar4@gmail.com (K.U.);
Tel.: +(604)-6533567 (K.U.); Fax: +(604)-6574854 (K.U.)
H.N.M.E.; Abdullahi, S.S.; Habibu, S.;
Jagaba, A.H.; Ibrahim, M.N.M.;
Ahmad, A.; Alshammari, M.B.; Abstract: In this work, a polypyrrole-polyethyleneimine (PPy-PEI) nano-adsorbent was successfully
Parveen, T.; Umar, K. Adsorption synthesized for the removal of methylene blue (MB) from an aqueous solution. Synthetic dyes
Behavior of Methylene Blue Cationic are among the most prevalent environmental contaminants. A new conducting polymer-based
Dye in Aqueous Solution Using adsorbent called (PPy-PEI) was successfully produced using ammonium persulfate as an oxidant.
Polypyrrole-Polyethylenimine The PEI hyper-branched polymer with terminal amino groups was added to the PPy adsorbent to
Nano-Adsorbent. Polymers 2022, 14, provide more effective chelating sites for dyes. An efficient dye removal from an aqueous solution was
3362. https://doi.org/10.3390/
demonstrated using a batch equilibrium technique that included a polyethyleneimine nano-adsorbent
polym14163362
(PPy-PEI). The best adsorption parameters were measured at a 0.35 g dosage of adsorbent at a pH
Academic Editors: Julio of 6.2 and a contact period of 40 min at room temperature. The produced PPy-PEI nano-adsorbent
Sánchez Poblete, Guadalupe del has an average particle size of 25–60 nm and a BET surface area of 17 m2 /g. The results revealed
C. Pizarro and Diego P. Oyarzún that PPy-PEI nano-composite was synthesized, and adsorption was accomplished in the minimum
Received: 5 June 2022
amount of time. The maximum monolayer power, qmax, for MB was calculated using the isothermal
Accepted: 27 July 2022 adsorption data, which matched the Langmuir isotherm model, and the kinetic adsorption data,
Published: 17 August 2022 which more closely fitted the Langmuir pseudo-second-order kinetic model. The Langmuir model
was used to calculate the maximum monolayer capacity, or qmax, for MB, which was found to be
Publisher’s Note: MDPI stays neutral
183.3 mg g−1 . The as-prepared PPy-PEI nano-adsorbent totally removes the cationic dyes from the
with regard to jurisdictional claims in
aqueous solution.
published maps and institutional affil-
iations.
Keywords: adsorption; methylene blue; polyethyleneimine; polypyrrole; wastewater

Copyright: © 2022 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
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Polymers 2022, 14, 3362. https://doi.org/10.3390/polym14163362 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 3362 2 of 20

to ecosystems and human life security. Water pollution from different dyes has become a
serious concern to human and marine life in recent years [1,2]. There are various types of
dyes used in the pulp, textile, clothing, fabrics, food, and pharmaceutical cosmetics sectors
can pose major problems by impeding sunlight penetration into the water and harming
aquatic life [3–5]. Complex aromatic molecules are more stable and difficult to biodegrade
than many artificial dyes [5,6]. Some dyes have been linked to allergies, skin irritation, and
even cancer in humans [7–9]. Therefore, environmental scientists and engineers must still
determine how to remove dyes effectively and comprehensively from water sources [10].
The most prevalent dye is methylene blue (MB), which is used to dye wool, silk, and
cotton, among other things. methylene blue adverse effects include eye burning, methe-
moglobinemia, trouble breathing, hyperplasia, convulsions, tachycardia, skin and gastroin-
testinal system irritation, nausea, diarrhea, and vomiting [2,10,11]. Furthermore, several
processes have been employed to remove dyes from wastewater or aqueous solutions,
including reverse osmosis, membrane filtration, ion exchange, adsorption, electrochem-
ical technologies, solvent extraction, chemical precipitation, and so on [12–14]. Except
for the adsorption approach, none of these technologies are routinely employed since
they are either expensive or ineffective. Adsorption has various advantages, including
lower startup costs, easy design, and quick functioning operation [15]. Furthermore, at
extremely low concentrations, the adsorption approach can eliminate particular or target
contaminants [16].
A large variety of adsorbent materials such as carbon material [17], chitosan [18,19],
nanocellulose [20], cellulose nanofibrils (CNFs), palm oil agriculture waste [21–23], cotton
stalk [24], jackfruit leaves [25], guava leaves [26], yellow passion fruit waste [27], neem
leaves powder [28], rice husk [29], and granular activated carbon (GAC) have been tested
in the removal of different dyes [30]. Because of their refractory and dangerous nature,
many dyes are not easily degradable and hence remain in water supplies for prolonged
periods of time [31]. Adsorption will provide high-quality water while being a cost-effective
solution. [32]. Nanomaterials and polymers are among the most promising new materials
for wastewater treatment. They have distinct functional features that may be tailored to
meet the needs of a variety of wastewater treatment systems. Polymer nanocomposites
are a specialized group of substances that provide greater performance by combining the
advantageous features of polymers with nanoparticles. Of course, the creation of these
kinds of functional materials necessitates a thorough grasp of their fundamental features
and the underlying science. Due to the presence of specific functional groups that might
mix well with diverse contaminants, polymers, for example, polypyrrole (PPy) and polyani-
line, as well as their composites, are getting broad consideration in ecological effluent
remediation [33]. For the clearing of various harmful dyes, such as Congo red, malachite
green, receptive blue, carmoisine, and others, some of these polymeric materials have al-
ready been examined for their activity, ease of combination, and the existence of a recovery
connection [34]. Because of their ease of synthesis, redox characteristics, and biocompati-
bility, PPy-based adsorbents have sparked a lot of scientific interest [35]. The removal of
dyes and their components by polypyrrole-directing polymer-based adsorbents has been
accounted for inconsistently, and scarcely any investigations have reported it [34,36]. The
use of composites made up of PPy and other materials for the elimination of reactive red
dye from an aqueous solution was reported in one study using -cellulose/polypyrrole
composites [34]. Recent studies using PPy/TiO2 MB dyes as a nano-adsorbent have shown
good adsorption capacity [34]. The fibrous adsorbents and decontaminated water might be
effortlessly isolated after the adsorption interaction since they have an enormous explicit
surface region, making adsorption on these adsorbents speedy and productive. Fibrous
adsorbents have been created as a reasonable option in contrast to run-of-the-mill ad-
sorbents like enacted carbon in the last ten years. Fibrous adsorbents are preferred to
conventional adsorbents because of their exceptionally active surface, satisfactory mechan-
ical strength, surface chemical change, pore size dispersion, and reusing capability [37].
Fibrous filters’ resistance to the flow of wastewater may be readily regulated. Several
Polymers 2022, 14, 3362 3 of 20

investigations have been conducted on the modification and conversion of typical textile
fibers into adsorbent structures capable of removing various substances from aqueous envi-
ronments, including textile dyes, heavy metal ions, and other hazardous compounds. The
dye removal efficiency of polypropylene (PP) nonwoven fabric was 88.72 percent [38], and
acrylic fibers modified with NaOH and citric acid are able to remove some selected heavy
metal ions from water efficiently [39]. The use of ethanolamine and diethylenetriamine
to modify acrylic fibers led in the creation of chelating fibers capable of removing Cr6+ ,
Pb2+ , Cu2+ , Ce3+ , and Ni2+ from aqueous environments [40,41]. Polyester fibers prepared
with formaldehyde and grafted with methacrylic acid demonstrated the capacity to adsorb
Cu2+ and Pb2+ from water [42]. Polyvinylamine-modified polyester fibers successfully
eliminated Cr6+ from polluted groundwater. Previously, an adsorbent was prepared by
grafting glycidyl methacrylate onto PET fibers and functionalized with iminodiacetic acid,
which demonstrated good removal effectiveness with two cationic dye solutions [38].
Although attempts have been made to recover MB from wastewater using PPy alone,
which has a poor adsorption mechanism for dyes and heavy metals, no attempt has been
made to extract methylene blue using PPy-PEI [43]. In the present study, a conducting
polymer of polypyrrole (PPy) and hyper-branched polymer (with terminal amino groups)
polyethyleneimine (PEI) formed (PPy-PEI) adsorbent was synthesized for the elimination
of harmful cationic methylene blue from commercial effluent. The adsorbent’s prepara-
tion conditions were crucial in the creation of an effective adsorbent for methylene blue
dyes from a watery solution. The effect of numerous limits on the adsorption’s working
conditions, such as adsorbent dosage, contact duration, beginning pH, and MB dye con-
centration, was explored, as well as the adsorption of isotherms and kinetic properties of
methylene blue dye adsorption on the PPy. The synthesized adsorbent is environmentally
friendly, efficient, and cost-effective, and it can readily be scaled up to large-scale use
without causing harm to the environment or human health.

2. Experimental
2.1. Materials
Methylene blue Sigma Aldrich (St. Louis, MO, USA), dye was used as the dyeing
agent (adsorbate) in the formulation of a stock solution with the formula C16 H18 N3 SCl,
as illustrated in Figure 1. Diluting 1.0 g of MB powder in a 1000 mL volumetric flask
filled with distilled deionized H2 O yielded a 1000 mg/L MB stock solution. Dilutions
of the stock solution were used to make the methylene blue -treated solutions with the
appropriate concentration.

Figure 1. Molecular structure of (a) MB (an adsorbate) and (b) PPy (adsorbent) and (c) (PEI).
Polymers 2022, 14, 3362 4 of 20

The monomer, pyrrole (99 percent), was distilled (purified) before use, and the oxidiz-
ing agent was ammonium persulfate (NH)2 S2 O8 . Polyethyleneimine (molecular weight:
1200–1300) was combined with distilled PPy to generate PPy-PEI polymer nano-adsorbent.
methylene blue stock solution was prepared with distilled-deionized H2 O; many of the
reagents were also provided by (Sigma-Aldrich) USA. Merck New Jersey USA provided
the HCl and NaOH necessary to adjust the pH.

2.2. Polypyrrole and Polypyrrole-Polyethyleneimine Synthesis

Based on the mole ratio of the oxidant to the monomer, the necessary amount of
oxidant was thoroughly dissolved in deionized water using sonication for five minutes.
Following that, the oxidant solution was combined with PPy solutions containing PEI and
slowly shaken for three hours at room temperature. A shift in the dye of the solution from
light green to black showed the growth of the products (PPy-PEI). The mixture’s black
substance was filtered, washed several times with deionized water, and then dried for
24 h at 65 ◦ C to remove extra reactants. As shown in Figure 2, the polymer product was
ground into a fine powder using a mortar and pestle before being sieved using a No. 120
US Standard Sieve to create a fine powder.

Figure 2. PPy-PEI nano-adsorbent’s synthesis design.

2.3. Characterization of PPy Nano-Adsorbents

A Perkin Elmer Spectrum spectrometer 400 (New Jersey, NJ, USA) equipped with an
FTIR microscope attachment, and a germanium crystal was used to obtain the ATR-FTIR
spectra of the PPy-PEI powder nano-adsorbent at ambient temperature.

2.3.1. Surface Analysis

Using N2 adsorption on a surface analyzer, a Brunauer–Emmett–Teller (BET) surface
study of PPy-PEI adsorbents was performed at 77.40 K. (1990, Sorptomatic Thermo Finni-
gan, Mundelein, IL, USA). The pore structure of this adsorbent was determined using
the t-method.

2.3.2. Thermal Property Measurement

A TGA analyzer (STA 6000 Perkin Elmer, New Jersey, NJ, USA) with a temperature
scope of 25 ◦ C to 800 ◦ C was utilized to play out the TGA-DTA investigation. The inves-
tigation utilized a nitrogen (N2 ) heating environment with a stream pace of 50 mL/min
Polymers 2022, 14, 3362 5 of 20

and a temperature pace of 10 ◦ C/min. For the adsorbents utilized in adsorption, a Differen-
tial Scanning Calorimetry (DSC) (TA DCS Q20 V24.10) was utilized under encompassing
nitrogen (20 cm3 /min) with a warming pace of 10 ◦ C/min.

2.3.3. Gel Permeation Chromatography

A Waters 2414 was loaded using a Gel Permeation Chromatography (GPC) device.
D-CCl4 was used as the eluent at 40 ◦ C with a stream rate of 1 mL min−1 , and a re-
fractive record identifier in order to calculate the molecular weight of the polypyrrole-
polyethyleneimine nano-adsorbent. Utilizing a defined adjustment bend and restricted
molecular weight polystyrene as a control, the Breeze register software was used to deter-
mine molecular weight.

2.3.4. X-ray Diffraction (XRD)

X-ray diffraction (XRD) studies were carried out using an X-ray diffractometer (Brand:
PAN analytical, model: Empyrean, Malvern, UK). Cu K radiation (=) was used to detect
XRD patterns in the 2-range of 5–90 2theta with a phase length of 1.25 s.

2.3.5. Morphological Analysis

The morphology of the PPy-PEI product was assessed using an energy-dispersive
X-ray spectroscopy (EDS or EDX) equipped field emission scanning electron microscope
(FE-SEM Type SU 8220 brand, Hitachi, Japan).

2.4. Batch Adsorption

Each experiment was run three times, and the mean was used to ensure accuracy.
Batch adsorption was done utilizing the created PPy-PEI adsorbents at known methylene
blue concentrations. Between 0.05 and 0.5 g/mL of adsorbent were employed in 25 mL
of MB at known concentrations. When the platform shaker reached an ideal pH of 6.2
at room temperature and a rotating velocity of 150 rpm in the pH range 2.2–12.2, the
effect of pH on MB adsorption was discernible. The initial C0 (mg/L) and final Ce (mg/L)
concentrations of methylene blue in this solvent at 664 nm were calculated using a UV-
visible spectrophotometer (Shimadzu, 2600, Kyoto, Japan) (1).

C0 − Ce
 
% Removal o f MB = × 100 (1)
C0

Qe = {(C0 − Ce )V }/m (2)

where m is the arrangement’s capacity in liters and V is the mass of the adsorbent in
grams. In 10-min augmentations, the influence of contact time (from 0 to an hour) on MB
adsorption was focused while all other parameters were maintained constant. Different
initial MB fixations (10–40 ppm) were applied at different temperatures (20, 40, and 60 ◦ C)
at a range of adsorbent focuses, pH, and contact lengths in order to study the effects of
temperature on MB adsorption.

3. Results and Discussion

3.1. Physical Characteristics of PPy-PEI
In PPy-PEI adsorption studies, the surface area is critical. Nitrogen adsorption–
desorption experiments were performed to evaluate the porous nature and specific surface
areas of the PPy-PEI nano-adsorbent material, as shown in Figure 3a. The primed nano-
adsorbent PPy-PEI’s physical characteristics are as follows. Particle size was estimated
to be between 25 and 60 nanometers. The generated PPy-PEI fine powder’s BET surface
area, pore volume, and pore size were 17.04 m2 /g, 0.017 cm3 /g, and 79.9, respectively,
as shown in Figure 3a. Following methylene blue adsorption, PPy-PEI exhibits a type-II
sorption isotherm with saturation at a relative pressure (P/P0) of 0.3, the volume of holes
reduced substantially to 0.018, the total quantity of N2 adsorbed at P/P0 1.0, and the BET
Polymers 2022, 14, 3362 6 of 20

surface area decreased to 13.94 m2 /g from 17.04 m2 /g. Furthermore, at a specific pressure
of roughly 0.82, adsorption isotherms exhibit steep behavior, showing that mesopores and
macropores exist on PPy/PEI [44]. The average adsorption pore size diameter ranged from
64 to 79 µm, demonstrating the microspore nature of the nano-adsorbent. The Ppy-PEI
chelate was efficiently formed between the nano-adsorbent and the methylene blue, as
evidenced by the decrease in surface area and pore volume [45].

Figure 3. (a) N2 gas adsorption/desorption isotherms of PPy-PEI (b) X-ray diffraction of PPy-PEI
before and after the adsorption process.

Figure 3b shows the PPy-PEI adsorbent’s XRD diffraction type during methylene blue
dye adsorption. The PPy-PEI displays a broad pinnacle focused at around 2θ = 26.12◦ prior
to methylene blue adsorption, showing the hazy properties of the PPy-PEI nano-absorbent,
which are primarily brought on by the equal periodicity of the polymer chain. The PPy-PEI
adsorbent showed a virtually equivalent expanding top with enlarged force after methylene
blue adsorption; however, it was seen to have shifted to a different location at 2θ = 25.04◦ .
Even though the expanding pinnacles were not very transparent but did become more
intense after the adsorption treatment, this adjustment of the expansive pinnacle combined
with the PPy-PEI reveals MB adsorption on the adsorbent of PPy-PEI [46].
The ATR-FTIR spectra of (a) PPy fine powder prior to adsorption, (b) methylene blue,
and (c) PPy following MB adsorption are shown in Figure 4. The usual PPy characteristic
peaks before adsorption include the bands at 795 cm−1 , 1041 cm−1 , 1165 cm−1 , 1308 cm−1 ,
1540 cm−1 , and 2682 cm−1 [41]. A noticeable broad peak at 3298 cm−1 in 4b revealed the
existence of OH and NH2 groups of methylene blue, whereas the acute peak at 1636 cm−1
was attributed to the unique aromatic rings. In the FTIR of methylene blue treated PPy
(after adsorption) in Figure 4c, the enormous PPy peak at 2682 cm−1 (before adsorption) dis-
appeared, and a few tiny peaks emerged at 2916 cm−1 and 2310 cm−1 in its place. Figure 4a
shows that the bands at 1540 cm−1 attributable to C-N pyrrole ring straightening (before
adsorption) shifted significantly to 1515 cm−1 after methylene blue adsorption [47] After
methylene blue adsorption, the bands at 1308 cm−1 owing to C-N in-plane deformation
and 1041 cm−1 due to N-H wagging migrated to 1286 cm−1 and 1018 cm−1 , respectively.
Field emission scanning microscopy was used to analyze the morphology of polypyrrole-
polyethylimine nano-adsorbent. The FESEM pictures revealed that PPy-PEI was success-
fully synthesized; it possesses tumor-like or cauli-like characteristics. Figure 5a depicts a
micrograph of the polypyrrole-polyethyleneimine powder formed before adsorption with
methylene blue, demonstrating that it was uniformly distributed over the polypyrrole
surface, while Figure 5b shows the energy dispersion X-ray analysis of prepared PPy-PEI
nano-adsorbent at 10 µm. Figure 5c, shows the graph of an EDX elemental analysis of
Polymers 2022, 14, 3362 7 of 20

the prepared nano-adsorbent. [48]. Because PPy-PEI has less aggregate formation, its
adsorption to methylene blue is stronger, as is the fine powder’s small nano size [49]. Using
the program “image J,” the average particle size was calculated by selecting a picture with
a resolution of 2.0 µm. Figure 5 shows PPy-PEI average particle sizes ranging from 25 to
60 nm, with an average maximum particle size distribution of 35–40 nm [46,50].

Figure 4. FTIR spectra of (a) PPy fine powder before adsorption, (b) MB, and (c) PPy after adsorption
of methylene blue.

3.2. Thermal Analysis

3.2.1. Thermogravimetric Analysis (TGA)
The temperature performance of the generated PPy-PEI adsorbent was investigated
using TGA (PPy-PEI). Figure 6 shows the samples’ first weight loss, which begins at
50 ◦ C and remains until nearly 200 ◦ C, resulting in a 17.37 percent loss of polypyrrole-
polyethyleneimine. The first lost mass at about 100 ◦ C can be attributed to the sam-
ple’s moisture content (the boiling point of water). The second mass loss of the pro-
duced polypyrrole-polyethyleneimine was about 31% at 510 ◦ C; this was related to both
polypyrrole-polyethyleneimine nano-adsorbent breakdown and heat deterioration of the
oligomeric or unsaturated group in the polymer nano-adsorbent. At 510 ◦ C, the slope of
the curve steadily reduced (50 percent weight loss). The heat breakdown of less than 46%
of the initial polymer mass in the last step after 510 ◦ C illustrates the strong thermal nature
of the polypyrrole-polyethyleneimine nano-adsorbent [50].

3.2.2. Differential Scanning Calorimetry (DSC)

A differential scanning calorimetry (DSC) study on the polypyrrole-polyethyleneimine
adsorbent with and without adsorption treatment was carried out in a nitrogen environment
at a heating rate of 10 ◦ C min−1 . The lack of a melting endothermic peak in the DSC
curve of PPy-PEI nano-adsorbent in Figure 7 highlights the nano-adsorbent’s amorphous
nature. The DSC thermogram for PPy-PEI showed a very wide exothermic peak at 240 ◦ C
after adsorption treatment, while no such wide-ranging peak was seen for polypyrrole-
polyethyleneimine nano-adsorbent before adsorption treatment. This energy hump coupled
with the PPy-PEI nano-adsorbent exhibits internal bond rearrangements in polymeric
polymers containing methylene blue dyes after adsorption treatment, leading to energy
release [46].
Polymers 2022, 14, 3362 8 of 20

Figure 5. FESEM image of (a) PPy-PEI before and (b) EDX image of prepared PPy-PEI; (c) EDX graph
showing elemental analysis of prepared Ppy-PEI.
Polymers 2022, 14, 3362 9 of 20

Figure 6. TGA graph representing the temperature-dependent thermal breakdown of PPy-PEI.

Figure 7. DSC curve of polypyrrole-polyethylimine.

3.3. Gel Permeation Chromatography (GPC)

Gel permeation chromatography (GPC) was used to measure the molecular weight
and molecular weight averages of the polymer as shown in Figure 8. (Water 2414 Refractive
Index Detector) [51]. The total weight of the polymer was divided by the total mass
number of molecules present, i.e., (Mn), and 1595 and 1578 were discovered for PPy-PEI,
respectively. The average molecular weight (Mw) of PPy-PEI was 1934. The polydispersity
index (PDI) for PPy-PEI was 1.21, suggesting that the polymer sample had a more evenly
distributed dispersion of polymer chains.
Polymers 2022, 14, 3362 10 of 20

Figure 8. Distribution of Molecular Weight of PPy-PEI.

3.4. Effect of Adsorbent Doses

An UV-visible spectrophotometer was utilized to concentrate on the methylene blue
dye adsorption by the PPy-PEI adsorbent at different portions. Figure 9a showcases the
measurement reactions. It shows that as focus rises, the absorbance unit falls until it arrives at
zero at the suggested level (0.35 g). As a result, as the adsorbent volume rises, the adsorption
potential increases, corresponding to an increase in active sorption sites. Figure 9b illustrates
the efficiency of the PPy-PEI adsorbent in removing MB from a 20-ppm starting methylene
blue solution at 0.05 to 0.5 dosages. When 0.35 g of PPy-PEI was introduced, the MB
was completely removed (100%) and no more adsorption occurred until the concentration
reached 0.5 g, indicating saturation. Due to the existence of more active sites on the nano-
adsorbent, the level of the end increased as the adsorbent part grew. The presence of extra
hyper-branched end groups (NH2 ) on the PEI may have contributed to the end level rising
when the adsorbent fraction was increased [52,53]. With increasing doses above saturation,
however, there was no increase in the percentage of dye reduction. The amount of PPy-PEI
in the body has no influence on methylene blue removal. The extra MB is most likely
concealing some PPy-PEI adsorption sites, which explains why. Agglomeration when
higher concentrations were used might be another explanation for the masking of some
active sites of the PPy-PEI adsorbent. Others have observed that various adsorbents have
similar adsorption tendencies for methylene blue dyes [12,36].

3.5. Impact of Initial pH

One important factor that affects the adsorption process and provides important details
regarding the adsorption mechanism is the initial pH of the adsorptive solution. Initial pH
regulates (1) the dye’s charge by controlling the protonation/dissociation of the dye’s func-
tional groups, (2) the adsorbent’s surface charge by managing the protonation/dissociation
of the surface functional groups, and (3) the speciation degree of hydration of heavy metals.
Because the adsorption process is initially pH dependent, electrostatic interactions and/or
complexation processes must be present. Since it can impact the dye adsorption process by
altering the surface charge of both the polypyrrole-polyethylimine and the methylene blue
dye’s ionization workouts, the initial (underlying) pH plays a vital effect during the whole
adsorption period. Figure 10 shows how beginning pH affects methylene blue adsorption
on the PPy-PEI adsorbent. Because protons compete with dye particles for available adsorp-
tion sites, pH 2.2 caused PPy-PEI to have a reduced expulsion rate (86.4%). The amount of
disposal increased significantly as the pH decreased, reaching its peak (100%) at pH 6.2.
methylene blue elimination increased once again at a pH of 12.2, most likely because of
MB cation precipitation. The methylene blue adsorption PPy-PEI adsorbent movement
Polymers 2022, 14, 3362 11 of 20

revealed a harmonic pH of 6.2 for optimal adsorption. methylene blue adsorption using
natural palygorskite and polydopamine microspheres yielded similar results [54,55].

Figure 9. (a) UV-visible spectrometer and (b) methylene blue elimination effectiveness.

Figure 10. Impact of pH on MB adsorption.

3.6. Impact of Contact Time

Using a 20 ppm methylene blue fixation at 20 ◦ C in balance at pH 6.2, the effect
of contact duration on adsorption term was evaluated (Figure 11). In the first 10 min,
the adsorption rate of methylene blue was high showing that the molecules methylene
blue and PPy-PEI had a strong affinity. Currently, over the surface, MB adsorption was
Polymers 2022, 14, 3362 12 of 20

almost homogeneous. After this point, the rate of adsorption gradually decreased until it
reached equilibrium at 40 min, which may have been caused by long-term methylene blue
dispersion into the nano-adsorbent PPy-PEI [56].

Figure 11. Effect of contact time on the effectiveness of methylene blue dye removal.

3.7. Impact of the Temperature

The effect of temperature on the adsorption of the adsorbent cycles was studied, as
shown in Figure 12, by changing the arrangement temperature from 20 to 60 degrees Celsius.
Adsorption productivity decreased with temperature, perhaps as a result of reduced surface
mobility, proving that the methylene blue time of adsorption on the adsorbent polypyrrole-
polyethyleneimine is exothermic. When employing other adsorbents, several studies found
comparable methylene blue adsorption behavior. They linked the shorter sorption cycle to
diminishing interactions between the methylene blue and the adsorbent in an advanced heat
environment [57,58]. Figure 13 also illustrates how methylene blue adsorption occurred at
5-min intervals.

Figure 12. Shows how the adsorption of MB is impacted by temperature.

Polymers 2022, 14, 3362 13 of 20

Figure 13. The images show MB solutions approaching adsorption equilibrium at 5-min intervals
(10–40 min).

3.8. Adsorption Isotherm

The trial data was fitted using the most renowned models of sorption (Freundlich
model, Langmuir model, and Temkin model). According to the Langmuir model, on a
uniform (homogeneous) surface, monolayer adsorption produces dye adsorption. The
Langmuir isothermic model is characterized by condition (3) in which kL (L/g) is the
material’s stable adsorption capacity and adsorption, and Qmax (mg/g) is the maximum
adsorption strength based on the total number of monolayers present. It was a plot against
Ce if Ce /Qe framed a straight line. Using the inclines and blocks, the bounds Qmax and kL
were established. Within a temperature range of 20 to 60 ◦ C, Qe max and kL decreased from
183.0 to 131.1 mg/g, and 0.27 to 0.22 L/g, respectively. Table 1 shows the highest R2 (0.994)
connection values at 20 ◦ C, demonstrating that the Langmuir model may be adjusted to
take into account the experiment findings.

Ce Ce 1
= + (3)
Qe Qmax Qmax k L

1
RL = (4)
1 + k L Ce

Table 1. Demonstrates the parameters of the isotherm model for the MB adsorption at vari-
ous temperatures.

Temperature
Isotherm Model Parameter
20 ◦C 40 ◦ C 60 ◦ C
Langmuir qm (mg/g) 183.3 146.5 131.4
kL (L/g) 0.27 0.24 0.22
RL 0.062 0.11 0.11
R2 0.994 0.886 0.929
Freundlich KF (L/g) 112.0 77.0 70.1
N 8.80 6.68 6.69
R2 0.897 0.845 0.800
Temkin A 0.063 0.192 0.228
B 2.830 2.153 2.473
R2 0.754 0.671 0.725
Polymers 2022, 14, 3362 14 of 20

This demonstrates that adsorption is favorable when RL = 0, unfavorable when RL > 1,

linear when RL = 1, and irreversible when RL = 0. In the paper, RL was found to be between
0.062 to 0.11, indicating a successful adsorption process. The following are the ways in
which adsorption on a heterogeneous surface affects the linearized Freundlich isotherm
adsorption articulation:
1
ln Qe = ln K F + ln Ce (5)
n
We use the Freundlich coefficients KF (L/g) and n, which independently display the
rate and adsorption power. Plotting ln Qe vs. ln Ce and determining n and KF from the
slope and intercepts resulted in a straight line. The expected values for n and KF were 8.80
to 6.69 and 112.0 to 70.1 L/g, respectively. The third kind is represented by the Temkin
isotherm in condition (6) [57].

Qe = B ln K t + B ln C e (6)

The binding constant at equilibrium, Kt , corresponds to the highest possible binding

energy. The adsorption pressure and the constant B are connected. When Qe was plotted
against ln Ce , a linear plot was created with a maximum R2 of 0.754. The Langmuir isotherm
correlates better than the other isotherms, according to Table 1’s analysis of the PPy-PEI
results for the MB.

3.9. Adsorption Kinetics

Using pseudo-first order (PFO) and pseudo-second order (PSO) kinetics, the rate and
mechanism of methylene blue dye adsorption were investigated. Comprehensive kinetic
of methylene blue adsorption tests at pH 6.2 and almost room temperature of 20 ◦ C were
conducted. The (PFO) rate model is expressed by Equation (7).

k1
log ( Qe − Qt ) = log Qe − t (7)
2.303
The maximal adsorption limit is (mg/g), the steady-state Lagergren scale adsorption
is (min−1 ), and the adsorption limit at time in minutes is (mg/g). The values and that
were calculated using the graph and the log plot incline (-) are displayed in Table 2. This
adsorption procedure does not satisfy the PFO demand mode since the R2 esteem is poor
and the conscious worth is significantly lower than the exploratory worth [58]. Equation (8)
describes how to represent the PSO rate model.

t 1 t
= + (8)
Qt k2 Q2e Qe

Table 2. Kinetic model parameters for methylene blue adsorption with the increase in initial concentration.

First-Order Kinetic Model Second-Order Kinetic Model

C0 Qe Exp
Qe Cal Qe Cal
(mg/L) (mg/g) k1 R2 k2 R2
(mg/g) (mg/g)
10 9.6 32.30 0.069 0.984 64.80 0.0421 0.997
20 19.5 95.02 0.044 0.903 100.30 0.0475 1.00
30 29.4 50.64 0.056 0.987 145.94 0.0972 0.999
40 38.9 17.69 0.060 0.865 172.88 0.3400 0.995

3.10. Reusability and Regeneration of the Methylene Blue Adsorbent

The adsorbent’s reusability is critical for its practical application. The recycling experi-
ments were carried out with 0.01 mol/L NaOH solutions for two hours at 180 rpm shaking,
producing a desorption efficiency of more than 91 percent after the fifth cycle. The results
of five desorption—adsorption tests are shown in Figure 14. The adsorbent’s methylene
Polymers 2022, 14, 3362 15 of 20

blue adsorption capability was preserved, indicating that the PPy-PEI adsorbent had high
regeneration and reusability.

Figure 14. Adsorption capacity of PPy-PEI nano-adsorbent in 5 desorption–adsorption cycles.

4. Comparative Profile with Previous Literature

In dye adsorption investigations, PPy or its mixture with other substances is employed.
Adsorption experiments of Acid orange 7 (AO7) using Polypyrrole/nano silica composite
(PPN/SiO2 ) were conducted, with adsorption effectiveness above 99.4%. The PPN/SiO2
characteristics were determined using XRD, FTIR, pHzpc, TGA, SEM, and TEM studies. The
kinetic data were fit using a PSO kinetic model; the rate constant K increased as temperature
increased, indicating that the adsorption was endothermic. The AO7 adsorption process
was intricate and regulated by both surface adsorption and particle diffusion, according
to the adsorption mechanism investigations. Additionally, the results suggest that for
low fixations, adsorption occurs by film dispersion, but at higher fixations, molecule
dispersion is the rate-determining step. The Langmuir isotherm was followed by the
harmony data, according to the isotherm parameters, with a MAC (maximum adsorption
capacity) of 181.4 mg/g [59]. Under optimum conditions (pH 9, starting RR or RB focus,
75 mg/L; PPy/Ze part, 1.8 g/L; temperature, 50 ◦ C), the PPy/Ze nanocomposite absorbed
86.2 percent of RB and 88.3 percent of RR from the designed arrangement. Both RB and RR
elimination from synthetic solution were better matched by the Freundlich isotherm model
with PSO kinetics [60]. Adsorbents made of PAN/PPy mat were employed to remove
cationic yellow dye from a watery solution. The adsorption limit increased when the initial
dye focus, adsorption capacity, and temperature increased, reaching a MAC 59.63 mg/g,
according to the adsorption findings. Adsorption energy analysis has shown that the PSO
model may also be employed to represent the adsorption interaction [61]. During the
oxidative polymerization of pyrrole, a conducting polymer called polypyrrole was applied
in situ to a cotton substrate (PPy). The resulting materials were used as quickly divisible
and reusable adsorbents for the expulsion of methylene blue (MB) in an alkaline medium
as a model of cationic dyes with an MAC of 3.30 mg/g. A few factors, including contact
time, adsorbent dose, temperature, starting dye concentration, and pH, were investigated
Polymers 2022, 14, 3362 16 of 20

for their effects on the adsorption interaction. The adsorption cycle was modeled using
the Freundlich isotherm model and the PSO active model. According to the study of
thermodynamics, MB adsorption by PPy is a logical, unrestricted, and exothermic cycle.
The substrate recovery focus revealed that, taking into account the recovery of methylene
blue for reusing, PPy applied to cotton materials could be reused for dye adsorption several
times with excellent results [43]. Using pyrrole polymerization with potassium persulfate
as an oxidant, a composite made of coffee bean waste (CGW) coated in semi-conducting
polypyrrole (PPy) was produced. A SEM analysis of coffee fibers revealed a homogeneous
coating of PPy spherical nanoparticles with sizes ranging from 200 to 300 nm. Fluid
adsorption studies using the Rhodamine B dye (RhB) were carried out on the composite in
its as-arranged state. On adsorption conduct, the effects of pH and initial dye concentration
(C0 ) were examined. The results demonstrated that at solubility pH, this material was an
excellent RhB dye adsorbent. The Redlich–Peterson model and the standard Langmuir
adsorption model correctly predicted the RhB adsorption isotherm at a controlled pH of
9.0, with an anticipated MAC of (qmax) of 50.59 mg of dye/g of composite [62]. Table 3
described the utilization of PPy and its combination for dye adsorption under various
testing conditions.

Table 3. Comparative profile of polypyrrole based adsorbent for the adsorption of dyes.

Type of Adsorbents Type of Dyes Experimental Conditions Adsorption Capacity References

(pH 9, initial RR or RB
Polypyrrole/zeolite Reactive blue (RB) and concentration, 75 mg/L; PPy/Ze Qmax (mg/g)
[60]
(PPy/Ze) reactive red (RR) dose, 1.8 g/L; and 122.32(RB) 116.53(RR)
temperature, 50 ◦ C).
temperature (25 ◦ C), contact
Sodium time, initial pH (7), adsorbent
Methylene blue 217.4/666.7 mg/g [63]
alginate/polypyrrole dosage (1–5 g/L), dye
concentrations (10–50 mg/L).
Polypyrrole/sugarcane Acid pH 3; contact time about 60 min;
100 mg/g [64]
bagasse, (PPy/SB) black-234 (AB-234) dose 0.05 g; initial conc. 10 mg/L
Polyacrylonitrile/
polypyrrole Yellow dye. 80 ◦ C, 3 h, 30 mg/L 59.63 mg/g [61]
(PAN/PPy)
1 g/L, contact time 90 min,
Initial AO7 concentration 10
Polypyrrole/nanosilica
Acid orange 7 (AO7) mg/L, shaking speed = 200 rpm 181.4 mg/g. [59]
composite
and temperature 328 K
and pH = 3)
Polypyrrole-coated
Methylene blue dye 3.9 mg/L, 45 ◦ C, pH 7400 min, 3.30 mg/g [43]
cotton textile
Polypyrrole/coffee 200 mg/L, pH 9, 120 min, 25 ◦ C
Rhodamine B dye 50.59 mg of dye/g [62]
grounds waste and 125 mg dose
Dosage 0.2 gm, pH 9 and
Polypyrrole
Reactive black 5 adsorption time 60 min, 100 mg/g [65]
nanostructures
Temp 650 ◦ C
Volume of the solution: 150 mL;
Initial concentration: 20 mg/L;
Polypyrrole Congo red 11.53 mg/g [66]
pH: pH6.55;. Adsorbent dosage:
1.73 g/L. Temperature: 25 ◦ C.
PPy-PEI pH of 6.2; contact time 40 min at
Methylene Blue 183 mg/g Present study
nano-adsorbents room temperature; dose 0.4 g
Polymers 2022, 14, 3362 17 of 20

5. Conclusions and Future Recommendations

Nano-adsorbents of polypyrrole and polyethyleneimine (PPy-PEI) were effectively pro-
duced in this study. In the presence of PEI, pyrrole is chemically oxidized. On the produced
nano-adsorbent, cationic methylene blue adsorption from aqueous solution was examined.
This work demonstrates that conductive polymers polypyrrole-polyethyleneimine can
adsorb the cationic MB dye. At a low temperature (20 ◦ C) and pH of 6.2, the adsorption
cycle ought to arrive at equilibrium (with 100% removal) rapidly. The results of the research
revealed that the group adsorption parameters, such as adsorption dose, initial pH, and
contact duration at room temperature, significantly impacted the viability of methylene
blue adsorption. The MAC of the methylene blue dye nano-adsorbents was achieved
at a pH of 6.2. By using FTIR and EDX analysis, it has been determined that PPy-PEI
contains nitrogen particles, which function as the active site for methylene blue adsorption.
Isothermic studies at various temperatures revealed that the Langmuir model could broadly
match the exploratory results, in contrast to Freundlich and Temkin’s isotherms. The most
extreme limit monolayer, qmax, for methylene blue was found to be 183.3 mg g−1 using
the Langmuir model. The pseudo-second request was more effective than the pseudo-first
request in addressing the adsorption data of the energy at various concentrations. The
nano-adsorbent polypyrrole-polyethyleneimine is an excellent choice for use in the removal
of the methylene blue dye from an aqueous solution.
Furthermore, the synthesized nano-adsorbent can be used as an efficient and reusable
adsorbent for the adsorption of synthetic cationic dyes from textile effluents. Future re-
search should investigate its potential use in treating very acidic industrial wastewater
containing organic dyes, for the dual benefit of enhanced adsorption and environmental
friendliness. In addition, more research on various modifying agents and synthesis proce-
dures should be conducted with the objective of improving its aqueous phase stability and
adsorption capabilities. Additionally, column studies, as well as batch studies, should be
utilized to explore the potential of the adsorbent for large-scale applications, and to further
implement the removal of industrial dyes from wastewater. Adsorbent adsorption and
regeneration research should be prioritized to cut costs and reduce adsorbent waste. As
a result, additional studies are needed to create alternative desorption and regeneration
processes that would limit the breakdown of conducting polymer adsorbents’ structure
and extend their lifespan. Since robust adsorbents are appealing for practical applications,
methods to improve the fundamental reliability of leading polymer adsorbents and their
composites should be investigated. Some of the studies that were examined provided no
information, while others described sophisticated, energy-intensive preparatory processes
that could not be accurately duplicated on a commercial scale. Using MB and various hues
of overall contaminated waste materials in many research sectors is crucial to reducing the
risk of optional tainting caused by the adsorption cycle.

Author Contributions: M.N.M.I., K.U. and A.H.B.: Conceptualization, A.H.B. and S.H.: Methodol-
ogy, writing-original draft preparation, visualization, investigation, A.H.B. and H.N.M.E.M.: material
synthesis and characterizations, A.A. and S.S.A.: Results interpretation, M.B.A., A.H.B., A.H.J. and
T.P.: Writing Reviewing and Editing, K.U.: Supervision, funding acquisition. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by Universiti Sains Malaysia for financial support (short-term
grant; 304/PKIMIA/6315580).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2022, 14, 3362 18 of 20

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