Inorganic Chemistry Communications 139 (2022) 109318

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Inorganic Chemistry Communications

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Short communication

Effective Removal of Methylene Blue from Wastewater Using Magnetite/

Geopolymer Composite: Synthesis, Characterization and Column
Adsorption Study
Rasha A. Al-husseiny a, b, *, Shahlaa E. Ebrahim a
a
Environmental Engineering Department, College of Engineering, University of Baghdad, Iraq
b
College of Engineering, Al Qasim Green University, Iraq

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

Keywords: In this work magnetite/geopolymer composite (MGP) was synthesized using a chemical co-precipitation tech­
Geopolymer nique. The synthesized materials were characterized using several techniques such as: “X-ray diffraction (XRD),
Methylene blue Fourier- transform infrared spectroscopy (FTIR), vibrating sample- magnetometer (VSM), field-emission scanning
Fe3O4
electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET) and
Adsorption capacity
Barrentt-Joyner-Halenda(BJH)” to analysis the structure and morphology of the geopolymer and the obtained
Kaolin
Artificial neural network composite. The analysis indicated that metal oxide predominantly appeared at the shape of the spinel structure of
magnetite, and that the presence of nano-magnetite had a substantial impact on the surface area and pore
structure of the geopolymer. Methylene blue adsorption on the MGC was investigated. The specific surface area
of the geopolymer and Fe3O4/geopolymer composite was determined to be 26.604 m2/g and 69.04 m2/g,
respectively. It was revealed that a mixture of Fe3O4 and geopolymer with percent 10% magnetite to geopolymer
had high adsorption performance on MB, with a removal rate of over 95%, which was much greater than that of
separate mesoporous geopolymers. The synthesized nanocomposites as promising adsorbents have a potential
application in the removal of dyes from aqueous solution. Langmuir and Frendulich isotherm models were used
to analyze the equilibrium data, the Frendulich model revealing a strong correlation coefficient. The kinetic
process’s results were in accordance with the pseudo-second-order model. Fluidization of mass was used to
demonstrate dye breakthrough curves under the influence of various operating conditions, and the actual results
fitted with the predicted data produced using an artificial neural network(ANN).

1. Introduction environment have been developed and evaluated in recent years, such as
coagulation [4], advanced oxidation [5], ultrafiltration [6],ion-ex­
The release of many dyes and pigments into the aquatic environment change [7], electrochemical treatment [8], photocatalytic degradation
as a result of rapid industrial expansion has made wastewater treatment [9], and adsorption [10,11]. Adsorption is a popular approach among
a difficult issue in environmental sciences. Water pollution produced by physicochemical processes because of its low cost, simple design, and
dyes has developed as a result of their widespread usage in fields such as reusability [12].As a result, dye removal has been explored using ab­
textiles, leather, chemicals, petroleum products, paper, cotton, wool, sorbents with various geometries and chemical compositions [13]. The
plastic, and pharmaceuticals, attracting the attention of the scientific study is concentrating on less expensive and “greener” options. Geo­
community [1,2,3]. Methylene blue (MB) is a basic dyestuff widely polymers have gotten a lot of attention because of their numerous
utilized in different sectors and is one of the most frequently used in­ interesting characteristics, including ionic exchange, and the environ­
dustrial dyes. As a result, for both environmental protection and the mentally friendly aspect of their manufacturing method [14]. Geo­
reuse of these unconventional waters necessitate the treatment of water polymers are networks or chains of mineral molecules linked by
polluted by these compounds. Various strategies for recovering haz­ covalent connections. It is made by reacting an alkaline liquid with a
ardous chemicals from effluent before releasing them into the aquatic geologically derived substance such as kaolin (metakaoline) [14,15],

* Corresponding author.
E-mail addresses: rasha83@wrec.uoqasim.edu.iq (R.A. Al-husseiny), shahlaa.ebrahim@coeng.uobaghdad.edu.iq (S.E. Ebrahim).

https://doi.org/10.1016/j.inoche.2022.109318
Received 22 December 2021; Received in revised form 10 February 2022; Accepted 15 February 2022
Available online 18 February 2022
1387-7003/© 2022 Elsevier B.V. All rights reserved.
R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Table 1 2.2. Methods

Chemical Composition of Kaolin.
Component Weight (%) 2.2.1. Alkaline solution
The alkaline liquid used in this study was a combination of hydroxide
SiO2 48
Al2 O3 34 salts, such as sodium hydroxide (SH), sodium silicate (SS) and silica gel
Fe2 O3 1.76 (SG). To achieve the necessary molarity. First, 1.53g of (SH) was added
TiO2 1.5 to the distilled water, and after (SH) dissolved completely, 4.615 g of
CaO 0.9 (SS) are added. At this point, the solution is placed on a stirrer, a mag­
0.3
netic rod is inserted into the solution, and the mixture is stirred at 80 ºC
Na2 O
MgO 0.6
K2 O 0.43 and 600 rpm. After (SS) had all dissolved, 2.79g of (SG) was added and
Cl 0.03 dissolved completely. Finally, the solution was cooled naturally to room
L.O.I 12.48 temperature.

2.2.2. Preparation of geoplymer

ground granulated blast furnace slag (GGBS)and fly ash [16], rice husk
The kaolin was calcined at 750 ◦ C for 3 h at a rate of 5 ◦ C/min and
[17] ash, etc. [18,19].A geopolymer is made up of a polymeric Si-O-Al
converted to metakaolin. 10.73 g of metakaolin was added to the alka­
framework with alternating silicon and aluminium tetrahedra linked
line solution and mixed for 15 min with a mechanical mixer at a speed of
together in three orientations by sharing all of the oxygen atoms [20].
approximately (3000 rpm). For molding the geopolymer pastes, plastic
For the unusual three-dimensional network structure of geopolymer-
molds with diameters of 2.1 cm and heights of 4.2 cm were used. The
based adsorbents, with fixed-size pores and pathways that allow
specimens should be demolded after one day in a specified condition at
various pollutants to flow through it, has lately gained attention [21].
lab temperature. These samples were then cured for 28 days in a specific
There are numerous studies for removal of methylene blue and other
condition [28] as shown in Fig. (1).
dyes by using geopolymer as adsorbent [22,23]. Recently, Many scien­
tists have been working to improve the adsorption characteristics of
natural materials and create high-quality adsorbents. A lot of synthesis
approaches have been developed to fix this problem. Precipitating 2.3. Preparation of magnetite/ geopolymer composite (MGP)
nanoparticles on the surface of the adsorbent was one of the most effi­
cient methods [24]. This alteration will increase the adsorbent’s surface Magnetite/geopolymer composite (MGP) was prepared by using a
area, mechanical strength, and chemical resistance, as well as its ca­ co-precipitation method [29]. After the curing procedure, the geo­
pacity to absorb contaminants [25,26,27]. The purpose of this study is to polymer was grinded to the desired size. Geopolymer samples were
efficiently synthesize of magnetite/geopolymer composite (MGP) and to rinsed in deionized water for 1 h at 60 ◦ C at 30 rpm. To prevent the
present the impact of geopolymer modification by precipitating nano- influence of hydroxide precipitation during adsorption, the samples
magnetite in boosting the adsorption capacity of MB. In this work the were washed numerous times with Deionized water before being fil­
synthesized materials were characterized using several techniques to trated and dried, until the pH of the washing water was set at 7 ± 0.5 for
analysis the structure and morphology of the obtained composite. at least 24 h.[30]. Then, at room temperature geopolymer was added
with size of 194 µm to 300 ml of solution containing 0.02 M.of
2. Methodology FeCl2 .4H2 O and (0.04 M) of (FeCl3 ⋅6H2 O). Under vigorous magnetic
stirring, the quantity of geopolymer was modified to achieve a Fe3O4/
2.1. Materials and method geopolymer mass ratio of 1:10. The pH was gradually increased to
around 10 by adding NaOH solution and stirring for 30 min. 2 hr were
2.1.1. Materials spent heating the suspension to 95◦ –110 ◦ C. The cooled magnetic
Kaolin (Al2Si2O5(OH)4)was supplied from local area (Dwaikhla, composite was washed multiple times with distilled water . The result­
Western Iraqi Desert), Table (1) present the result of wet analysis for ing materials were separated from water using a simple magnetic pro­
chemical composition of kaolin, sodium silicate (Na2SiO3⋅5H2O), so­ cess and dried in an oven at 110 ◦ C.[24]. The processes for preparing the
dium hydroxide NaOH, and silica gel SiO2 (Thomas Baker). These ma­ MGP are represented in Fig. (2).
terials were used as starting materials to synthesize geopolymer ferric
chloride hexa-hydrate (FeCl3⋅6H2O, 98%, Thomas Baker), ferrous
chloride tetra hydrate (FeCl2⋅4H2O, 99%, Alpha chemika) were used in 2.4. Characterization techniques
precipitation of magnetite on the surface of geopolymer. Methylene Blue
(MB) with molecular weight: 373.90 g/mol, 98 % dye content) (Thomas In this work the synthesized materials were characterized using
Baker company) All of the other chemicals and reagents were analytical several techniques such as “Brunauer-Emmett-Teller (BET), Barrett-
grade and were utilized without being purified. Joyner-Halenda (BJH), field emission scanning electron microscopy
(FESEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction
analysis (XRD), Fourier- transform infrared spectroscopy (FTIR), and
vibrating sample-magnetometer (VSM)” to analysis the structure and
morphology of the obtained composite.

Fig. 1. Synthesis of geopolymer.

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 2. Preparation of magnetite / geopolymer Composite.

2.5. Isothermal equilibrium experimentations filtered and examined. After repeating the process at 400, 600, and
1000 rpm, the concentration time decay curves were produced by
Various weights of MGP (0.0.25, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, plotting the Ce/Co vs. time.
and 0.4) g were utilized in, 100 ml volumetric hipflasks.Methylene blue
solution with a concentration of 50 mg/L were prepared, and each 2.6.1. Adsorption kinetics models
hipflask received 50 ml of the solution. 0.1 M sodium hydroxide (NaOH)
or hydraulic acid (HCL) were used to adjust the pH of solutions to the 2.6.1.1. Pseudo-first-order kinetic model. This model may be expressed
desired value.A shaker set at 200 rpm was used to agitate the mixture with reliability using the Lagergren equation. It describes how the MB
constantly for 2 h. Centrifuge were used to filter each sample. A UV adsorps MGP kinetically [34]. The following equation represents the
spectrophotometer was used to quantify the ultimate equilibrium con­ model [35]:
centrations. The equilibrium MB uptake (qe, mg/g) and removing effi­
dq
ciency (%) were estimated using Eqs. (1) and (2), respectively [31,32]. = k1 (qe − qt ) (5)
dt
V(Co − Ce)
qe = (1) where qt (mg/g) and qe (mg/g) are the solute amounts adsorbed at
W any given time t (min) and equilibrium, respectively. The pseudo-first
Co − Ce order rate constant is k1 (min− 1). Take integration of.Eq. (2), depend­
Removalefficiency% = 100( (2) ing on the boundary conditions of qt = 0 at t = 0 and qt = qt at t = t, the
Co
equation becomes Eqn 6 [35]:
Where, Co and Ce (mg/L) are the beginning and final MB concen­
trations, respectively; VL is the volume of the solution, and W (g) is the ln(qe − qt) = lnqe − (K1 t) (6)
weight of the adsorbent utilized. To find the isotherm constants, the A plotting graph of ln (qe – qt) versus t can yield the slope (k1) and
collected data was fitted using two models.. The Langmuir equation can intercept (log qe). The equilibrium MB solute uptake (qe) and first order
be expressed as followsEqn 3: kinetic constant (k1) can eventually be determined.
qm *KL *Ce
qe = (3) 2.6.1.2. Pseudo-second-order kinetic model. The pseudo second-order
1 + KL *Ce
model is represented by the equation below. As illustrated below in
Where qe is the solid-phase equilibrium concentration (mg/g), Ce is
Eqn 7, the mass transfer of driving force, (qe - qt), is proportional to the
the MB liquid equilibrium concentration in solusion (mg/l), KL is the
number of unoccupied sites. [36]:
equilibrium constant associated to binding site affinity (l/mg), and qm is
the maximum quantity of MB per unit weight of adsorbent for full sur­ dq
= k2 (qe − qt )2 (7)
face coverage. Adsorption on a heterogeneous surface with varying dt
adsorption energies is explained by the Freundlich isotherm. The Taking integration of Eq. (4) whilst considering boundary conditions
Freundlich constant KF represents the change in adsorption energy with of qt = 0 at t = 0 and qt = qt at t = t, the equation converts to Eqn 8:
surface coverage (qe) in Eq. (4).[33]
1 1
= + k2 t (8)
qe = KF Ce1/n (4) (qe − qt ) qe
Where KF is a rough estimate of adsorption capacity. where k2 is a second-order rate constant. To illustrate a linear rela­
tionship, rearrange Eq. (5) as follows in Eqn 9:
2.6. Kinetic experiments
t 1 t
=( 2+ ) (9)
qt k2 qe qe
The adsorbent type is used in a kinetic process to determine the
optimal mixing speed for removing 95% of the MB and to determine the The connection between t/qt and t yields the slope (1/qe) and
best kinetic adsorption model to explain the experimental results. A intercept 1/(k2qe2). Finally, the second order rate constant (k2) and the
Pyrex glass beaker with a volume of 2 L was used for kinetic process amount of adsorbed dye per mass of composite at the final equilibrium
experiments. In the beaker, 1 L of MB aqueous solution at 50 mg /L was point (qe) are determined.
added and the pH was set to 7. The beaker cell’s center was fixed with a
three-bladed stainless-steel axial flow impeller. At room temperature, 2.6.1.3. Intra-particle diffusion model. Weber and Morris proposed intra-
the impeller’s agitation was begun at 200 rpm. The exact weight of particle diffusion model, which can be written as Eqn 10 [37]:
adsorbent was applied at zero time interval. At various time periods,
samples from the beaker were obtained. The ultimate equilibrium qt = kid t1/2 + C (10)
MB concentration of these samples was determined after they were

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 5. FT-IR analysis for a) Fe3O4, b) Geopolymer, c)MGP, and (d) MGP after
removal MB.
Fig. 3. The schematic diagram of experimental equipments.
2.7. Continuous experiments

Table 2 The fluidized bed adsorber experiments were conducted in a glass

Surface and pore characteristics of the Geopolymer and MGP. column with a 5 cm I.D. and a height of 100 cm, with a distributor and a
Characteristics Geopolymer MGP small mesh sieve at the bottom for uniform fluidizing and bearing par­
2
Specific surface area (m /g) 26.604 69.04
ticles in the column, and the influent solution was introduced to the
External surface area of pores (m2/g) 95.145 154.06 column through a plastic pipe from the bottom. Fig. (3) shows a sche­
Total pore volume (cm3/g) 0.2372 0.2166 matic representation of the experimental apparatus. After computing the
Volume of mesoporous and macroporous (cm3/g) 6.1124 15.862 hydrodynamic parameter (minimum fluidized velocity Umf), column
BJH adsorption cumulative surface area of pores (cm2/ 29.201 52.053
experiments were performed to determine the MB’s breakthrough curve.
g)
BJH adsorption average pore diameter (nm) 35.656 12.551 Different static bed heights (5 cm, 7.5 cm, and 10 cm) with three
distinctive flow rate conditions (10,15, and 20 L/ h, with adsorbent bed
particle diameters: (0.15–0.25 mm) were studied in continuous testing.

3. Results and discussion

3.1. Characterization of materials

Table (2) lists the BET surface properties of the gopolymer and MGP.
The characteristics of geopolymer were enhanced when the nano­
particles were precipitated. MGP improved the initial geopolymer sur­
face area by 62 % while increasing the pore volume by 61%.
Furthermore, following precipitation, the geopolymer’s adsorptive
properties, such as pore surface area, enhanced. These improvements
are the first indication that MGP may operate as an adsorbent. MGP has
a mesoporous structure with diameters ranging from 2 to 50 nm, ac­
cording on its pore structure value.
The magnetite, MGP, and geopolymer XRD patterns were presented
in Fig. (4). The crystalline phases quartz, as well as an amorphous
structure with a high level of reflection at 2θ between 15 and 40◦ , can be
identified in the geopolymer [17,39]. XRD diffraction peaks for geo­
polymer at 2θ = 20.136◦, 21.03◦, 25.487◦, 26.823◦, 29.54◦, 30.66◦,
36.75◦, 39.65◦, 42.63◦, 50.35◦, 59.985◦, and 68.247◦ are shown in this
Figure with reference code of (00–038-0471). The XRD diffraction peaks
for MGP are shown also, including the reference code (01–081-0537).
Fig. 4. X-ray diffraction (XRD) pattern for structure of (a) Synthesized Fe3O4
magnetite is responsible for the variation in intensity noticed in the
(b) Synthesized Geopolymer and (c) Crystalline structure MGP.
peaks at 30 and 36◦ on the MGP sample [40].
The FTIR spectroscopic analysis of magnetite, gepolymer, and MGP
Where qt (mg/g) is the quantity adsorbed at time t (s), Kid (mg/g s1/
at the 400–4000 nm wavelength range was used to confirm the existence
2) is the intra-particle diffusion rate constant, and C is the value of the
of functional groups that could be responsible for the adsorption process,
intercept, which indicates the thickness of the boundary layer; the
as shown in Fig. (5). The peak at 583 nm in the FTIR of magnetite (Fig. 5-
bigger the intercept, the greater the boundary layer impact. The linear
a) is connected to the Fe–O group. The development of two asymmetric
plots of qt against t1/2 with zero intercept show that the total rate of
bands between 467 and 786 nm was detected by FTIR studies (Fig. 5),
adsorption is determined by intra-particle factors [38].
which is indicative of the spinel structure of magnetite [41]. The O–H
stretching and H–O–H hydrogen-binding water peaks in the

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 6. VSM analysis for (a) the synthesis magnetite and (b) MGP.

Fig. 7. FESEM image for (a) Synthesized geopolymer (b) MGP(c) MGP after adsorption of MB.

Fig. 8. EDS analysis for a) Synthesized geopolymer, b)MGP (c) MGP after adsorption of MB.

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 9d. Effect of initial concentration on adsorption of MB.

Fig. 9a. Effect of pH on adsorption of MB.

Fig. 9e. Effect of agitation speed on adsorption of MB.

Fig. 9b. Effect of amount of sorbent on adsorption of MB.
significant bands between 3750 and 2900 nm, indicating that the car­
boxylic group is (OH). Peaks near 2800–2920 nm correspond to the
(C–H) stretching vibration of alkane groups, while peaks near 424, 723,
1029, 1633, and 3441 nm correspond to the (C–Br, C–O, C– – O, and
OH) stretching vibration of alkyl carbonates, halides, aromatic com­
pounds, alcohols, amines, carbonyl, and hydroxyl groups, respectively.
A vibrating sample magnetometer (VSM) with a magnetic field of 6
kOe was used to investigate the material’s magnetic properties. VSM
analysis of synthesized Fe3O4 and MGP is shown in Fig. (6), a and b. The
magnetization of the produced Fe3O4 revealed that it was magnetic and
completely attracted the magnet. This substance had a magnetization of
70 (emu/g). Due to the low amount of Fe3O4 incorporated into the
geopolymer structure, which was equal to 10%, the magnetization of the
synthetic MGP was substantially lower than that of pure synthesized
Fe3O4 [43].
The FESEM images for, synthesized geopolymer, and MGP before
and after adsorption of methylene blue are shown in Fig.(7 a-c). The
Fig. 9c. Effect of contact time on MB removal.
shape and surface morphology of this synthesized material were inves­
tigated using FESEM. The surface of the geopolymer was uniform and
geopolymer’s FTIR spectra at 2925.49 and 3451 nm, respectively. The
coarse, with irregular aggregates., as seen in Fig. (7-a). There were
presence of hydrate (H2O), hydroxyl (–OH), ammonium, or amino is
several tiny cavities and holes found. This was a good indication that
indicated by this band. It should be followed by the presence of spectra
geopolymer can operate as an excellent magnetite nanoparticle support
in the 1600–1300, 1200–1000, and 800–600 nm ranges for hydroxyl
surface. Fig. (7-b) shows the geopolymer after precipitation of nano­
compounds [42]. The H–O–H deformation peaks at 1642 nm. The
material on its surface with an average size of 36 nm spherical shape, It
peak at 1024 nm is caused by Si–O–Si deformation, while the sharp
also consists of a number of aggregates that are not uniformly separated.
peak at 831 nm is caused by Si–O stretching of quartz and silica, the
Furthermore, the exterior surface of MGP is riddle with deep ravines and
peak at 526 nm is caused by Al–O–Si deformation, and the peak at 457
grooves. In reality, the morphological characteristics of the MGP surface
nm is produced by Si–O–Si deformation [55]. FTIR measurement of
are advantageous because they give a greater surface area for adsorbate
MGP following MB adsorption is shown in Fig.( 5.d). The results
molecule sorption as shown in Fig. (7-c).
demonstrate that dye adsorption on the surface of MGP increases the
The energy dispersive X-ray spectroscopy (EDS) analysis of the
transmittance. However, FTIR spectroscopic analysis revealed
synthesized geopolymer and the megnetite/geopolymer composite

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Table 3
Compares the adsorption capacity of MB dye and the influence of geopolymer development in this study to previous researches.
Adsorbent Type Concentration Adsorbent dose pH Contact time Adsorption capacity References

macrofungi spent mushroom waste 50 mg/L 0.55 mg/100 ml 8 4 hr 239.818 mg/g [44]
fly ash geopolymer monoliths 1–50 mg/L (0.11–0.55) (2–12) 30hr 15.4 mg/g [49]
Clay and rice husk 25 mg/L 4 3 20–80 min 15.95, 17.89 and 20.22 mg/g [50]
GP-1 and GP-2 and GP-3
MKG (5–60 mg/L) 0.1 g/100 ml (2–13) 2 hr 43.48 mg/g [15]
LD Slag (50–150) mg/L 0.25 g/L to 2 g/L 4–9 0–200 min 86 mg/g [51]
Fly Ash –based geopolymer spheres (10–250)mg/L (1–2.5)g/ 0.2L – 24 hr 30.1 mg/g [52]
Magnetite /geopolymer composite MGP (10–100)mg/L 0.2 mg /50 ml 7 30 min 76.34 mg/g This study

[44,45].
Table 4
Isotherm models parameters for Methylene blue.
3.2.2. The impact of dose
Model Parameters MB Using a variety of adsorbent quantities, the effect of MB adsorption
Langmuir qm(mg/g) 76.34 on the quantity of adsorbent (MGP) dosage was investigated (0.025 to
KL(l/mg) 0.233 0.4 g). Each dosage was added to 50 ml of aqueous contaminant solution
R2 0.9186 and continuously mixed under the following conditions: Co = 50 mg/L,
RL 1.163
Freundlich KF, 13.6
pH = 7, agitation rate = 200 rpm, and contact time = 1 h in a batch test.
n-1 0.537 Fig. (9b) illustrates the effectiveness of removing of MB as a function of
R2 0.9903 MGP quantity. The results show that increasing the adsorbent dosage
within the prescribed range improves removal efficiency. This trend was
predicted because it is general knowledge that the higher the sorbent
before and after removal of methylene blue are illustrated in Fig. (8 a-c),
dose in a solution, the much more active sites are available. However, it
respectively. The EDS data showed that the chemical composition had
appears that adding 0.2 g to 50 ml of contaminated solution is enough to
changed: geopolymer elemental content were Si, O, Al and Na as shown
achieve equilibrium [46].
in Fig. (8-a). This content of elements were changed in the EDS analysis
for MGP of (Si, Al, O, Na, Fe, and Cl). The EDS analysis of MGP decreased
3.2.3. The impact of contact time
and the The high mass ratio of Fe and O components emphasized the
The proportion of MB adsorbed was calculated at various contact
effective interaction of geopolymer with magnetite nanoparticles. The
times while all other factors remained constant. The relationship
EDS analysis of MGP after adsorption of MB presented the content of MB
elements (C, S and N) as shown in Fig. (8-c).

3.2. Batch experiments

3.2.1. The impact of pH

By changing the pH of the solution from 2 to 11, the impact of pH on
the adsorption of MB onto magnetite/geopolymer was investigated. The
experiments used 50 ml of MB with an initial concentration of 50 mg/L
and 0.2 g of sorbents, with a contact time of 1 hr. It is clear that the
amount of adsorption is influenced by the pH of the solution. As shown
in (Fig. 9a). A higher MB removal efficiency (98.8%) was obtained at pH
7, The removal of MB by MGP showed lower removal performance at the
pH range from 2 to 6, this can be attributed to the number of positively
charged surface sites on the adsorbent at the acidic range as more
carboxyl and siloxane groups in the adsorbent bind H+ which affect
through electrostatic repulsion and resulting in the adsorbent and it
Fig. 11. Concentration decay curves of MB in batch experiment.
became more difficult to bind to the MB dye ions. This is consistent with

Fig. 10. Langmuir and Fruendlich isotherm models.

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 12. Kinetic models.

between removal efficiency and different contact times is depicted in

Table 5 Fig. (9c). The MB sorption increases with increasing contact time and
Kinetic models parameters for Methylene blue.
remains stable after reaching equilibrium at 30 min. This might be
Model Parameters MB related to the adsorbent particles’ high surface area being available in
qe experiment (mg/g) 12.225 the early stages of the adsorption process. The rate at which the adsor­
Pseudo-first-order qe cal(mg/g) 9.78 bate is transferred from the exterior to the interior sites of the adsorbent
K1 (1/min) − 0.3812 particles manages the uptakes rate when the surface sorption sites get
R2 0.984
exhausted [44].
Pseudo-second qe (mg/g) 12.422
order K2(g/mg.min) 0.1339
R2 0.9996 3.2.4. The impact of initial concentration
Intra-particle Diffusion C 10.193 Other tests looked at the influence of different initial MB concen­
kid(mg/g.min) 0.2275 trations (Co) on sorption effectiveness. Co concentrations ranging from
R2 0.4258
10 to 100 mg/L were used in these experiments, as well as with 0.2 g/50
ml MGP, and the mixture was shaken for 30 min at 200 rpm with an
initial pH of 7. The removal efficiencies for as a function of Co at
equilibrium state are shown in Fig. (9d). The results demonstrate a
higher removal efficiency at lower Co concentrations, with a declining
trend at increasing Co concentrations up to 100 mg/L. The saturation of
the sorbent’s active sites that interact with MB might be considered as
the cause of these differences [47].

3.2.5. The impact of agitation speed

The agitation speed is an important parameter in the sorption pro­
cess. Fig. (9e) shows the effect of agitation speed on removal efficiency
of MB. The result show that higher removal efficiency are 98.6 % at
agitation speeds 200 rpm,250 rpm and 300 rpm respectively and lower
removal efficiency at agitation speeds 150 rpm reach to 90.%. This may
be attributed to trying of shaking speed to contain all the available
binding sites. However, higher speed usually create turbulence condi­
tion and reduce time available for contact between adsorbate and
adsorbent. The non-homogeneity of the sorption mixture as a result of
the vortex phenomena is considered to be the cause of the activity at
Fig. 13. Experimental data and theoretical breakthrough curves for MB lower agitation speeds [48].
removal at various bed weights, Co = 10 mg /L, dp = 0.15–0.25 mm diameter. Results indicated that one of the more effective ways was to

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R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

Fig. 14. Error computations in ANN model based on the testing sample.

precipitate magnetite on the surface of the geopolymer. In compared to 3.4. Continuous process results
utilizing simply geopolymer or other materials, this modification
improved the adsorbent’s surface area, mechanical strength, and In the column study, theoretical minimum fluidized velocity (Umf)
chemical resistance, as well as its capacity to absorb MB (see Table (3)). calculated using Eq. (12) [54].
μl (ρl − ρp)g
3.3. Mathematical models Umf = [√(33.7)2 + 0.0408dp3ρl − 33.7] (12)
dpρp μl2
3.3.1. Isotherm models According to Eq. (12), the minimum fluidization velocity (Umf) and
In order to determine the isotherm constants, the collected data was minimum flow rate were calculated as 0.1715 mm/s and 1.21 L/h,
fitted using two models. Linear fitting to the experimental data yielded respectively, producing motion and uniform mass transfer of pollutants
the parameters for each model. Table(4) summarizes all the parameters from bulk liquids to the surface of the adsorbent, and the optimal flow
and their respective determination coefficients.Fig. (10) present linear rate used in this investigation was 10 L/h. As shown in Fig. 13, the
fitting to the experiments data Table(4) indicated that Freundlich breakpoint time to establish equilibrium for the MB was decreased by
isotherm model was the best-fit model to describe the sorption of MB on utilizing a lower bed height. As demonstrated in Figs. 13 and Fig 14, data
the MGP with higher determination coefficients R2 of 0.99.3. Value of n from MB in a continuous study were well fitted with expected data
greater than unity indicates a favourable adsorption taking place [52]. generated by an artificial neural network in IBM SPSS software version
This indicated that the adsorption occurs under a multilayer and het­ 26.
erogeneous surface for MB.
4. Conclusion
3.3.2. Kinetic models
The typical concentration decay curves of MB in batch experiment In comparison to the geopolymer as presented in the study, magne­
are shown in Fig. 11 at different agitation speed which represents the tite was precipitated on the surface of the geopolymer to improve their
relation between Ce/Co and different contact times. The optimum performance in pollutants removal. This alteration increased the ad­
agitation speed needed to achieve Ce/Co = 0.05 was (400) rpm for MB. sorbent’s surface area, mechanical strength, and chemical resistance pH
The optimum mass of adsorbent (WA) necessary to achieve 95 % value, efficient contact duration and molecular weight, adsorbate mol­
removal performance for a liter of MB solution (Co = 50 mg/L at room ecules, initial MB concentration, and agitation speed are all important
temperature) with a final equilibrium concentration of C/Co = 0.05 was variables in the removal of methylene blue solution by magnetite/geo­
2.18 g, as calculated using the isothermal and balancing equations for polymer composite. The presence of more negative and energetic func­
solute as shown in Eq. (11) [53]. tional sites on the surface of MGP, different pore sizes in the adsorbent’s
structure, and having various different active compositions (detected by
VL(Co − Ce)
WA = (11) FTIR) are the main reasons for the adsorbent’s performance in MB
KF C1/n
e
removal and demonstrating higher removal rates compared to MB
Where WA is the low mass of adsorbent, VL is the volume of the so­ removal by synthesized geopolymer only as reported in the literature.
lution, Co and Ce (mg/L) are the beginning and final adsorbate con­ This adsorbent is more economically feasible to operate, cost effective
centrations, respectively, KF is a rough estimate of adsorption capacity. and friendly environment.
The adsorption kinetics of MB onto MGP was investigated using pseudo
first order, pseudo second order and intra-particle diffusion models as Declaration of Competing Interest
shown in (Fig. 12), using the experimental data at various initial con­
centrations. The calculated parameters values obtained from the appli­ The authors declare that they have no known competing financial
cation of three models are tabulated in Table (5). By comparing R2 for interests or personal relationships that could have appeared to influence
each applied model and the compatibility between the estimated and the work reported in this paper.
observed qe values, the most favourable model may be identified. The
pseudo 2nd order R2 value are greater than other models, and the qe cal Acknowledgment
values for MB are considerably closer to the qe expirement for MB than
other kinetic models. The authors are thankful to the University of Babylon /material en­
gineering college / Ceramic laboratories staff for the assistance provided
for this study.

9
R.A. Al-husseiny and S.E. Ebrahim Inorganic Chemistry Communications 139 (2022) 109318

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