Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Performance Assessment: Influence of Sorbate-Sorbent Interphase Using Magnetite Modified Graphene Oxide to Improve Wastewater Treatment Olayinka Oluwaseun Oluwasina1,2.
Mochamad Zakki Fahmi1*, and Olugbenga Oludayo Oluwasina3 Department of Chemistry.
Universitas Airlangga.
Kampus C Mulyorejo.
Surabaya 60115.
Indonesia Department of Marine Science and Technology.
The Federal University of Technology.
B 704.
Akure 340110.
Nigeria Department of Chemistry.
The Federal University of Technology.
B 704.
Akure 340110.
Nigeria * Corresponding author:
email: m.
fahmi@fst.
Received: February 20, 2023 Accepted: May 20, 2023 DOI: 10.
22146/ijc.
Abstract: The adsorption of brilliant green onto magnetite-graphene oxide nanoparticles (MGONP.
from an aqueous solution was explored via batch experiments.
The adsorption properties of MGONPs were carried out under various experimental conditions related to pH, contact time, adsorbent dose, temperature, and initial adsorbate The adsorption capacity of MGONPs and optimum pH were 54.
57 mg gOe1 and 6, respectively.
Equilibrium was attained after 30 min, and the adsorption kinetics data best fitted the pseudo-second-order.
The Freundlich isotherm best fits the Acetone was able to desorb the dye from the loaded adsorbent.
Additionally, the newly developed adsorption attributes effective surface area .
SBET) and dimensionless preferential adsorption .
were more accurate than the conventional specific surface area (SBET).
The adsorption capacity provides information about the sorbate-sorbent interface .
The relevance and accuracy of the new parameters for future adsorption system design by correlation analysis were validated.
This study confirms the successful modification of MGONPs for the sorption of the cationic dye brilliant green.
Keywords: magnetite-graphene oxide nanoparticles.
preferential adsorption.
surface area.
effective surface area.
brilliant green n INTRODUCTION The use and discharge of dye in waterbody have created toxicity risks for humans and aquatic creatures.
The dye's color prevents sunlight penetration into the water body, resulting in a loss of primary productivity.
Dye molecules can be classed based on their ionic charge, which can be zwitterionic, anionic, non-ionic, or cationic .
It has been reported over the years that there are more than 100,000 different synthetic dyes that are commercially available, with a yearly production of more than 700,000 metric tons .
It was revealed that about half of the applied dye was present in the effluent after analyzing the chemical composition of textile dye effluents.
The high concentration of colors in wastewater from textile manufacturing has been connected to the low absorption properties of fibers of dyes .
The complex molecules that make up synthetic dyes are typically composed of azo.
Olayinka Oluwaseun Oluwasina et al.
triphenylmethane, or heterocyclic/polymeric structures, and due to their stability, they can last for a very long time in the natural ecosystem without changing or being The excessive use of these dyestuffs has become a growing source of environmental concern.
During production and use, more than 10 to 15% of dyes are released into the environment .
A million tons of azo dyes are estimated to be produced annually on a global scale.
For a healthy ecology, a sustainable economy, and excellent health, there must be access to high-quality water.
Lack of access to clean water is a severe issue in both industrialized and developing Water that contains trace levels of color .
ess than 1 mg/L) is visibly unpleasant and inappropriate for irrigation, domestic use, or human eating .
Brilliant green (BG) is a cationic triaryl methane dye that comes in a yellowish-green powder.
Because its Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
color change from green to yellow at pH 2.
BG can also be used as an indicator, a biological stain in veterinary medicine, and a stabilizer in poultry feed to limit fungi attacks .
Exposure to this dye may cause gastrointestinal and respiratory tract issues and systemic dermatitis in humans, resulting in nausea, vomiting, diarrhea, cough, trouble breathing, and jaundice .
BG is toxic to aquatic life with long-term Brilliant green has been used as an antiseptic on the skin, but it is harmful when it comes into contact with the eyes.
Sedimentation, filtration, oxidation, electrochemical techniques, adsorption, and ion exchange have all been employed to remove dye from aqueous solutions .
Among the different methods utilized, adsorption has several advantages, including simplicity, high adsorption capacity, low cost, and environmental friendliness .
The use of nanoparticles for dye removal from wastewater has been investigated by various researchers .
Magnetite nanoparticles have recently received a lot of interest because they are inexpensive, environmentally acceptable, and easy to produce.
These particles also exhibit excellent optical, chemical, and electrical properties and significant superparamagnetic capabilities.
However, these particles agglomerate easily and oxidize quickly .
The aqueous dispersion of iron nanoparticles is improved by embedding them on sheets of carbonaceous materials, and graphene-based materials are kind of promising carbonaceous substances for such purposes .
Graphene oxide (GO)-based nanomaterial synthesized with iron nanoparticles exhibited improved dispersion behavior in water .
When graphite is oxidized, oxygen functional groups are introduced into the structure, making it hydrophilic and allowing it to form a stable suspension in aqueous conditions.
GO is made by sonicating graphite oxide in water to exfoliate it.
The high surface area of GO enables the incorporation of a wide range of functionalization groups into the sheets .
Graphene-based composites are formed by incorporating various functional groups, thereby improving the materialsAo photocatalytic, biocidal.
Olayinka Oluwaseun Oluwasina et al.
electroactive, and capability .
Chemical modification of graphene-based materials has been used to develop nanocomposites with improved dispersion and compatibility in aqueous conditions.
The integration of magnetite with graphene or GO may be a promising method for the removal of pollutants.
Synthesis of magnetite-GO has recently been produced and utilized for drug delivery .
, magnetic-based imaging .
, and pollutant treatment from wastewater .
Magnetite-GO was synthesized for pollutant removal because of its stability and performance high.
However, there is no integrative report on the adsorption efficiency of brilliant green upon nanocomposite of magnetite-GO.
Thus, in the present research, we focused on studying the design of magnetite-based nanocomposite material that can effectively remove emerging contaminants even when they are present in low concentrations (Scheme .
The adsorption properties were examined by studying the effect of pH, the adsorption kinetics, and the adsorption isotherms to identify the adsorption mechanism.
The study gives a novel assessment of the adsorbents' performance by computation of newly developed physical features, which shed light on the effect of the sorbents' physical and chemical properties and sorbates on the separation process.
As a result, the statistical estimations used to assess the sorbents' efficiency are also presented.
The interaction between the sorbent and sorbate is also carefully considered in relation to the contaminant's sorption.
n EXPERIMENTAL SECTION Materials Chemicals such as graphite powder .
m, syntheti.
, sulfuric acid .
H2SO.
, hydrochloric acid .
HC.
, hydrogen peroxide .
H2O.
, potassium permanganate (KMnO.
, ferrous ammonium sulfate, ammonium ferric sulfate, aqueous ammonia, sodium hydroxide pellets and brilliant green (BG.
C27H33N2AHO4S) were purchased from Sigma-Aldrich and used without further purification.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Instrumentation UV-Visible absorption spectra of the sample obtained by UV-Vis-NIR spectrophotometer UV-3600 (Shimadzu.
Japa.
The morphology of MGONPs was determined by Ultra PLUS Field Emission Scanning Electron Microscopy instrument (Zeiss.
German.
, and functional group data of the nanomaterial provided by Fourier transform infrared spectrometry Spectrum 100 spectrometer (PerkinElmer.
USA).
The textural properties, surface area and porosity of the material were measured with a Tristar II 3020 analyzer (Micromeritics.
USA).
Procedure Synthesis of graphene oxide The synthesis of modified GO was prepared using the method reported by Oluwasina et al.
About 4 g of graphite, 2 g of sodium nitrate, and 92 mL of concentrated H2SO4 were mixed with magnetic stirring in an ice bath to give a black slurry.
KMnO4 .
was added slowly to keep the temperature below 5 AC.
The suspension was removed from the ice bath and heated to 35Ae40 AC for 90 min.
A 190 mL of deionized water was then added, and the temperature was adjusted to 98 AC for 20 min.
40 mL of 30% H2O2 was added to the mixture .
he mixture turned bright yello.
The mixture was diluted with 200 mL of deionized water and stirred for 30 min.
The reaction product was centrifuged and washed with Milli- Q water and 10% HCl solution until the pH was neutral.
The product was vacuum dried at 60 AC for 48 h and stored for further characterization and application.
Synthesis of magnetite-graphene oxide nanoparticles Magnetite-graphene (MGONP.
were prepared by co-precipitating iron oxide magnetic nanoparticles decorated on GO.
Briefly.
GO .
was dispersed in deionized water .
mL) and Next, about 10.
7 g ammonium ferric sulfate and 58 g ferrous ammonium sulfate were dissolved in 100 mL of deionized water under oxygen-free conditions.
After that, 10 mL aqueous ammonia was added into the solution to give iron oxide nanoparticles, with the addition of GO.
The reaction was stirred for 45 min at 85 AC and cooled at room temperature.
The resulting MGONPs were collected by a magnet and washed with water and anhydrous ethanol, dried at 70 AC for 12 h in a vacuum oven.
Adsorption study To obtain the concentrations required, working solutions of BG were produced from the stock solution, which is prepared by dissolution of BG .
on deionized water .
p to 1 mg dmOe.
Batch adsorption was performed by agitating 25 cm3 of BG solutions of known concentration at a given temperature with a sorbent dosage of 10 mg, and the pH was changed by Scheme 1.
Schematic illustration of MGONPs and the adsorption process of BG Olayinka Oluwaseun Oluwasina et al.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 1.
Adsorption isotherm models investigated for the sorption of BG onto MGONPs
Isotherm model
Equation* Langmuir
q bC
1 bC
Freundlich
K C
Sips Temkin
Dubinin-Radushkevich
Redlich-Peterson
Khan
q bC
1 bC
ln A C
RT ln 1
K C
1 a C q b C Parameters Reference qm, b KF, n .
qm, b, n .
AT .
qm, .
KRP, aRP, g qm, ak, bk 1 b C *qeq is the adsorption capacity .
g gOe.
Ceq is the adsorbate equilibrium concentration in solution .
g dmOe.
qm is the maximum monolayer capacity .
g g-.
b is the Langmuir isotherm constant .
m3 mg-.
KF is the Freundlich isotherm constant .
g gOe.
m3 mgOe.
n is the intensity of adsorption intensity.
AT.
Temkin isotherm equilibrium binding constant .
m3 gOe.
Temkin isotherm constant.
Dubinin-Radushkevich isotherm constant .
ol2 kJOe.
KT.
Redlich-Peterson isotherm constant .
m3 gOe.
Redlich-Peterson isotherm aRP.
Redlich-Peterson isotherm constant.
Khan isotherm exponent.
Khan isotherm constant adding either 0.
1 M NaOH or HCl.
The final concentration of the dye after filtering was determined at 624 nm ultraviolet-visible (UV-Vi.
The effects of pH, adsorbent dosage, temperature, and initial BG concentrations were investigated to identify the best adsorption conditions.
The adsorption capacity was calculated by the Freundlich.
Langmuir, and Sips models, respectively, presented in Table 1.
Eq.
were used to calculate the adsorption capacity .
and efficiency, respectively.
E C A C eq E
EE C 100%
E Ci A % A adsorbed A EE i q eq A A C Ci A C eq where Ci represents the initial adsorbate concentration .
g dmOe.
, qe is the adsorption capacity .
g gOe.
Ceq is the equilibrium concentration of adsorbate .
g dmOe.
V is the adsorbate volume .
, and m is the mass of adsorbent .
Adsorption isotherms The adsorption isotherms were investigated with BG concentrations ranging from 10 to 100 mg dmOe3.
Aliquots Olayinka Oluwaseun Oluwasina et al.
of 25 cm3 of varied concentration were introduced to 40 mg of adsorbents and shaken for 4 h in a thermostated shaking water bath at 298 K.
The equilibrium concentration of BG in the suspensions was determined using UV-Vis spectrophotometry after 4 h.
To analyze the equilibrium data, the isotherm models in Table 1 were used.
Adsorption kinetics Adsorption kinetics was investigated by mixing a 25 cm3 aliquot of a 20 mg dmOe3 BG solution with a 40 mg adsorbent dosage.
The time intervals for contacting the solutions were in the range of 5Ae300 min.
UV-Vis spectrophotometry was used to determine the final concentration of BG after filtering.
The experimental adsorption data attained through the batch studies were applied to the pseudo-first-order, pseudo-second-order.
Elovich kinetics, and intraparticle diffusion models given in Table 2.
Desorption experiment The desorption experiment was carried out by mixing 30 mg of the adsorbent with 25 cm3 aliquots of 20 mg dmOe3 BG solution for 3 h.
After that, the mixture was filtered through a Whatman No.
1 filter paper, and Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 2.
Adsorption kinetics model explored for the removal of BG onto MGONPs Kinetic model Pseudo-first-order Equation* Pseudo-second-order k q t 1 k q t Parameters qeq, k1 Reference .
k2, qeq kid, c k t / ln 1 t , .
Elovich Oe1 *qeq is the amount adsorbed at equilibrium .
g g ), qt is the amount adsorbed at adjusted times .
g gOe.
, k1 is the pseudo-first-order rate constant .
inOe.
, k2 is the pseudo-second-order rate constant .
mgOe1 minOe.
, kid is the intraparticle diffusion rate constant .
g gOe1 min0.
, is the Elovich parameter defined as the desorption constant .
mgOe.
, is the Elovich parameter defined as the initial adsorption rate .
g gOe1 minOe.
Intraparticle diffusion n the filtrate was analyzed for BG.
The adsorbent that was filtered off was dried at 60 AC.
After that, 20 mg of the BG loaded-adsorbent was added to a 25 cm3 acetone and shaken for 12 h.
The filtrate was analyzed using UV-Vis spectrophotometry after the mixture was filtered.
SEMEDX and FTIR were used to examine the loaded and desorbed adsorbent to evaluate if the dye had desorbed from the adsorbent surface.
There was a significant change as the dye was desorbed on the surface of the Characterization of the Synthesized Material The textural features of MGONPs were determined using N2 adsorption-desorption isotherms.
This provides information on the sample's pore volume size distribution and specific surface area.
The pore volume determined according to nitrogen adsorption by the specified method applies only to mesopores and does not consider macropores (> 50 n.
Therefore, the pores could be grouped into micropores (< 2 n.
, mesopores .
Ae50 n.
, and macropores (> 50 n.
The result indicates that MGONPs are mesoporous, having an average pore diameter of 14.
13 nm.
The pore volume determined according to nitrogen adsorption by the specified method applies only to mesopores and does not take into account macropores (> 50 n.
addition, the adsorbents exhibited type IV isotherms and Data analysis Using routine nls in the R statistical computing environment, the adsorption data were fitted into the adsorption isotherms and kinetics models.
The modelAos effectiveness was determined by looking at the sum of squared residuals (SSR) and residual squared errors (RSE).
The SSR of the model with the lowest SSR was chosen.
dV/dlog(D) Pore Volume .
mA/.
Quantity Adsorbed .
mA/g STP) RESULTS AND DISCUSSION .
Relative Pressure (P/P.
Pore Diameter .
I) Fig 1.
BET Nitrogen adsorption-desorption isotherms and .
BHJ pore volumes of MGONPs Olayinka Oluwaseun Oluwasina et al.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
H3-Type hysteresis loops, indicating that the nanomaterial is mesoporous .
Type IV represents an adsorption isotherm with hysteresis related to capillary condensation in mesopores.
MGONPs showed a large surface area of 116.
81 m2 gOe1, having a BarrettAeHalendaAe Joyner (BHJ) based pore volume of 0.
3763 cm3 gOe1 (Fig.
The FTIR spectrum displayed in Fig.
2 appears the functional groups on the surface of MGONPs.
The absorption peak at around 598 cmOe1 can be referred to as the FeAeO vibrational mode of Fe3O4 nanoparticles.
The absorption peaks at 3604 and 1692 cmOe1 correspond to the extending vibration of AeOH and AeFeOO, respectively .
This finding demonstrates that Fe3O4 successfully decorated the GO surface, as confirmed by SEM In addition, the FTIR spectrum shows three broad peaks at 1749, 1565, and 1031 cmOe1, which correspond to the aromatic C=O stretch.
C=C, and C-H stretching, respectively .
The peaks around 1938, 2091, and 2331 cmOe1 correspond to the peaks of the dye molecules on the adsorbent.
The morphology of MGONPs was investigated using SEM, as shown in Fig.
The MGONPs have a C=O .
7 cm-.
% Transmittance C=C .
0 cm-.
O-H .
0 cm-.
Fe-O .
Wavenumber .
Fig 2.
FTIR spectra of MGONPs before adsorption Fig 3.
SEM and EDX images of MGONPs .
after adsorption, 2.
5 m scale and .
desorption of BG, 2.
5 m scale Olayinka Oluwaseun Oluwasina et al.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Sorption Characteristics Batch adsorption tests for BG adsorption onto MGONPs were carried out to investigate the adsorbent's adsorption characteristics and efficiency in removing BG.
pH, adsorbent dosage, contact time, temperature, and initial adsorbate concentration were all investigated as sorption parameters.
The experimental data were also used to investigate adsorption isotherms and kinetics.
Desorption tests for the dye were carried out to see if the adsorbents could be regenerated and reused.
Effect of pH A solutionAos pH influences the dye structure and the adsorbent nature due to the ionization behavior and changes in surface charge, respectively .
The experiment pH was studied by varying the pH from 3 to 10 .
1 g of adsorbent and 10 mg dmOe3 BG concentration for 300 min contact time at 180 rp.
because at pH O 2, the BG dye solution became colorless.
The disparity of color concentration could result from its extended conjugated system of alternate double and single bonds.
The reaction between OHOe ions and BG molecules occurs with conjugation interruption at higher pH values.
The reduced color following increased pH may happen due to the central carbon atom of BG acting as an electrophilic center, and the OHOe is favored.
The dye's rate of color change was faster in alkaline media, which could be attributed to its high nucleophilic nature.
Decolorization of the dye could also occur through nucleophilic attack by H3O , but the color fades more slowly in an acidic medium.
A colorless compound is formed at low pH because H3O destroys the conjugation between the aromatic rings .
Fig.
4 depicts the The removal of BG was increased by increasing the pH to a maximum pH of 6 .
%) and then decreased to reach a minimum removal percentage at pH 9 .
%).
Olayinka Oluwaseun Oluwasina et al.
BG removal (%) crumpled surface.
This might be the effect of the quick drying of the liquid phase from the MGONPs during the preparation process.
Also, small granular particles were observed on its surface, where Fe3O4 deposits.
The SEMEDX images revealed that the dye molecules were adsorbed on the surface of the adsorbent during Fig 4.
Effect of pH on the adsorption of BG .
25 cm3 of 10 mg dmOe3 BG, 5 h equilibration time, 10 mg sorbent dose, agitation speed of 180 rpm, temperature 298 K) was discovered that the removal percentage in acidic environments is lower than in neutral environments.
This could be due to the partial dissociation of surface functional groups in an acidic BG solution, resulting in electrostatic repulsion between the BG and MGONPs .
The reduction in the alkaline environments related to the neutral and acidic environment could be attributed to the higher electrostatic repulsion between the MGONPs and the dye molecules .
Given the structures of graphene's sp2-bonded carbon particle, it is anticipated that a AAeA interaction may play a critical part in the adsorption of natural fragrant compounds on MGONPs.
There are a parcel more oxygen-containing useful bunches on the surface of MGONPs, and these bunches can work as electronwithdrawing bunches, localizing electrons from the A framework of graphene and interferometer with the AAeA scattering strengths between the fragrant ring and The oxygen-containing functional groups repressed the adsorption of natural chemicals on carbon materials by means of water adsorption, dispersiverepulsive intelligence, and hydrogen holding, in this way driving the lower adsorption capacity of MGONPs .
Effect of dosage By varying the mass of MGONPs from 10 to 120 mg, the effect of dosage on BG removal from aqueous solution was examined (Fig.
The result showed that the Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
BG removal (%) Dose .
Fig 5.
Effect of adsorbent dose on the sorption of BG .
onditions: 25 cm3 of 20 mg dmOe3 BG, 4 h equilibration time, pH 6, agitation speed of 180 rpm, temperature 298 K) percentage adsorbed increases as the adsorbent dose For example, using 10 mg of MGONPs, a removal percentage of 46% was initially attained and then rose to 70% when the dosage was increased to 40 mg.
After then, it increased to 75%, with no discernible increase in the percentage adsorbed.
This could be because the nanocomposite agglomerated, reducing the surface area accessible for adsorption .
Furthermore, as the MGONPs dosage was increased from 10 to 40 mg, the BG percentage removal increased remarkably.
This can be attributed to an increase in the number of unoccupied adsorption sites and functional groups on the adsorbent surface.
This indicates that 40 mg has the necessary number of active sites to achieve maximal pseudo-second-order, intraparticle diffusion, and Elovich models.
The linear findings for the four kinetic models are shown in Fig.
7, and the kinetic parameters of the fitted models are listed in Table 3.
Pseudo-secondorder model better explained the adsorption of BG onto MGONPs.
The experimental qe values obtained are near the calculated values for both pseudo-first-order and pseudo-second-order models.
The results of these models revealed that BG adsorption on MGONPs occurred via a biomolecular interaction involving the exchange or sharing of electrons between the adsorbent and the dye.
As a result, the sorbent's adsorption capacity is related to its surfaceAos number of active sites .
The following steps are involved in explaining the diffusion mechanism of adsorption processes: .
transfer BG removal (%) Olayinka Oluwaseun Oluwasina et al.
Time .
Fig 6.
Effect of contact time on the sorption of BG .
onditions: 25 cm3 of 20 mg dmOe3 BG, 40 mg sorbent dose, speed of 180 rpm, pH 6, temperature 298 K) Kinetics study Experimental data Pseudo-second-order t/qt The removal of BG from MGONPs was investigated to establish the equilibrium sorption time, with time intervals ranging from 5 to 300 min.
Fig.
6 shows the percentage of BG adsorbed onto the sorbent as a function of time.
The percentage adsorbed onto MGONPs increases as the contact time increases, from the results After 30 min, the equilibrium was reached, with a maximum removal of 60%.
After that, there was no discernible change in the BG concentration, indicating that the adsorption sites had been saturated .
The adsorption kinetics of BG using MGONPs were studied using four kinetics models: pseudo-first-order.
Time .
Fig 7.
Pseudo-second-order kinetic model Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 3.
The calculated parameters for the four kinetics models tested for the sorption of BG onto MGONPs at different time intervals Pseudo-second-order Intraparticle diffusion Elovich Parameters qeq/mg gOe1 cal/mg gOe1 k1/10Oe2/min qeq/mg gOe1 k2/10Oe3/g mgOe1 minOe1 kid/mg gOe1 minOe0.
/mg gOe1 minOe1 /g mgOe1 Conditions: 25 cm3 of 20 mg dmOe3 BG, pH 6, 40 mg adsorbent, agitation speed 180 rpm, temperature 25 AC of the adsorbate from the bulk solution to the surface of the solid phase.
passage through the liquid film attached to the solid surface .
ilm diffusio.
internal mobility by pore dispersion from the surface of the solid phase to the inner surface of the permeable structure .
ntraparticle diffusio.
diffusion of the solute on the adsorption sites of the solid phase bringing about physisorption and chemisorption on the surface of the solid phase .
The intraparticle diffusion show was utilized to decide the rate-limiting step of the method.
the event that a direct plot that passes through the origin is gotten, adsorption is said to happen as it were by intraparticle diffusion .
It is presumed that two or more stages regulate the process if a linear plot that does not pass through the origin is obtained.
The linear graphs obtained in this investigation passed through all the dots for pseudo-second-order, which indicates that the model is suitable for the experimental data.
Adsorption isotherms Over a concentration range of 10 to 100 mg dmOe3, the influence of initial BG concentration on adsorption onto MGONPs was examined.
As the dye concentration increased, the percentage of dye removed decreased (Fig.
This could be owing to the fixed number of active sites available for BG molecules on the adsorbent.
At higher dye Olayinka Oluwaseun Oluwasina et al.
g g-.
Model Experimental Pseudo-first-order Concentration .
g/dm-.
Fig 8.
Effect of initial concentration on the adsorption of BG onto MGONPs .
onditions: 25 cm3 of 10 to 100 mg dmOe3 BG solution, 40 mg adsorbent dose 4 h equilibration time, pH 6, agitation speed of 150 rpm, the temperature of 298 K) concentrations, the active sites of the adsorbent become saturated, and the adsorption capacity is thus determined by the initial concentration .
The equilibrium adsorption isotherm is required to determine the interacting behavior between the adsorbent and the adsorbent.
It is also essential for the adsorption system's strategy.
The Langmuir adsorption isotherm assumes that the binding sites are evenly distributed across the sorbent surface and have a similar affinity for single molecular layer sorption.
The bonding to the sorption sites might be chemical or physical, but it must be sufficiently strong to prevent the adsorbed molecules from being displaced .
According to the Freundlich adsorption isotherm, sorption occurs on a heterogeneous surface, implying multilayer This means that as the starting concentration of the solution is increased, the adsorbate concentration will rise .
The Langmuir and Freundlich models were used to fit the experimental equilibrium data.
The slope and intercept of each equilibrium graph were used to calculate the Langmuir and Freundlich parameters (Fig.
Table 4 appear the adsorption isotherm parameters for models that fitted the test balance information for BG The Freundlich isotherm best fits the Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Qe .
g/dm.
Qe .
g/dm.
Ce .
Ce .
Fig 9.
The Langmuir .
and Freundlich .
adsorption isotherms fitted the experimental data for the sorption of BG onto MGONPs Table 4.
Isotherm modelsAo parameters Isotherms Freundlich
Langmuir
Sips Temkin
Dubinin-Radushkevich
Redlich-Peterson
Klan
Parameters kF/mg gOe1
SSR*
RSE*
qm/mg gOe1
b/dm3 mgOe1
SSR
RSE
SSR
RSE
SSR
SSR
SSR
Value *SSR: sum of squared residuals.
*RSE: residual squared error information based on the whole of SSR gotten.
The Freundlich isotherm demonstration is based on the Olayinka Oluwaseun Oluwasina et al.
wonders of heterogeneous surfaces with a few adsorption components included, where KF and n are the Freundlich constants related to the adsorption capacity and adsorption concentrated, respectively.
The Freundlich parameter, n, shows the adsorption When the adsorption intensity, n < 1, it shows the favorability of the adsorption intensity over all the concentration ranges studied, but if n E 1, it shows that the adsorption intensity is favorable at high concentrations but less at lower concentrations .
The experimental data obtained for MGONPs shows an n value greater than 1, indicating that adsorption is favorable at higher concentrations but less at lower According to the Langmuir model, qm 57 mg g-1.
On the other hand, the Freundlich model yielded an adsorption intensity value of 1.
indicating a successful adsorption process .
The Langmuir adsorption capacities .
of MGONPs were stacking up with various reported adsorbents for the removal of BG.
Table 5 shows that the removal .
by MGONPs used in this study compares favorably with other adsorbents.
The Langmuir model results in some parameters that can be used to estimate the favorability of the adsorption process.
The separation factor (RL), was calculated by using Eq.
RL A
1 A bC i .
where Ci denotes the initial BG concentrations .
g dmOe.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 5.
Comparison of adsorption capacity of various reported adsorbents and b denotes the Langmuir constant .
m3 mgOe.
The value of RL can be used to calculate the sequestration process's favorability.
If 0 < RL < 1, adsorption is assumed to be favorable, unfavorable if RL > 1, irreversible if RL = 0, and linear if RL = 1 .
All RL values obtained in this study were found to fall between 0 < RL < 1.
hence, the removal of BG onto MGONPs showed favorable The procedure is more favorable when RL values are minimal (Fig.
Preferential adsorption The special sorbate adsorption .
and viable surface region .
SBET) are the novel adsorption properties calculated for the performance evaluations.
The found eSBET is noteworthy since, notwithstanding the general SBET of the adsorbent, chemical species adsorption pivots on the number of germane dynamic locales with a great fondness for the sorptive.
The determination of eSBET gives data on the importance of the dynamic locales to the q and, more essentially, the qp esteem.
Most of the considerations inspected within the current work did not allow data with respect to the sorts or sums of chemical functionalities on the sorbents.
As a result, it is expected that the eSBET will rise directly as long as the pertinent chemical surface usefulness is shown on the SBET, either Table 6 appears the calculated adsorption parameters and highlights from the literature.
The adsorbent's mass adsorption capacity .
, mg Oe1 g ) for a particular dye serves as the primary indicator for determining the extent of the sorbate-sorbent interphase.
Only 2 of the 22 studies (Table .
showed qp values greater than 1, indicating that the sorbates preferred the sorbent to remain in the solution.
The highest values were reported Olayinka Oluwaseun Oluwasina et al.
Temperature/K qm/mg gOe1 Reference .
This study Adsorbent Hydroxyapatite/chitosan composite Luffa cylindrical sponge Corncob biochar Areca nut husk Poly(AN-coVP)/Zeolite composite MGONPs Concentration .
g dm-.
Fig 10.
Separation factor RL of BG onto MGONPs by Li et al.
(SN = 18.
qp = 49.
ZnO nanoparticles on Congo re.
and Lv et al.
(SN = 19.
qp = 336, sodium alginate/graphite based on malachite gree.
, respectively.
Fig.
11 shows a plot revealing the trend in the reported and derived adsorption properties for the selected adsorbents and pollutants.
The dataset's correlation data are shown in Table 7.
After looking into the analyses, we found that the correlations increased noticeably.
The q for brilliant green and the other adsorbates showed a similar trend with eSBET .
61 and 81.
19%) than with SBET .
88 and 58%), respectively.
The negative correlations between SBET and eSBET demonstrate that an adsorbent's adsorption capability is not always correlated with its SBET.
Inclusive, the derived adsorption properties .
p and eSBET) are much more consistent for equitable comparison between studies with various experimental settings and research goals.
The moles of the sorbent and qp value of the adsorbate over solubility performed a positive Therefore, the more the sorbate's mass transfers onto the adsorbent, the higher the sorbent mass Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 6.
Estimated adsorption features of the various experiments S/N Dye Sorbent mass .
ol gOe.
Congo red Malachite green Methylene blue Neutral red Methyl orange 75y10Oe4 11y10Oe4 71y10Oe3 86y10Oe4 43y10Oe5 15y10Oe3 93y10Oe4 03y10Oe6 01y10Oe5 48y10Oe4 30y10Oe4 59y10Oe4 93y10Oe4 68y10Oe4 96y10Oe4 28y10Oe4 13y10Oe4 02y10Oe4 36y10Oe3 75y10Oe4 06y10Oe3 53y10Oe5 Surface .
2 gOe.
Effective Surf.
Area .
ol mOe.
63y10Oe6 06y10Oe4 45y10Oe6 01y10Oe7 44y10Oe8 75y10Oe4 81y10Oe5 21y10-08 02y10Oe6 16y10Oe6 91y10Oe7 58y10Oe6 57y10Oe7 48y10-07 88y10Oe7 19y10Oe6 68y10Oe7 83y10Oe5 10y10Oe5 55y10Oe6 55y10Oe5 58y10Oe7 Moles of .
75y10Oe6 11y10Oe6 71y10Oe5 49y10Oe4 43y10Oe5 38y10Oe3 97y10Oe5 01y10Oe8 01y10Oe6 04y10Oe5 73y10Oe4 03y10Oe4 93y10Oe5 84y10Oe5 48y10Oe5 64y10Oe5 52y10Oe6 09y10Oe6 68y10Oe5 37y10Oe6 30y10Oe6 27y10Oe5 Volume (L) Solubility .
ol LOe.
29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 29y10Oe4 66y10Oe6 10y10Oe5 Moles in (Sorbent/So.
29y10Oe4 29y10Oe4 29y10Oe4 14y10Oe3 29y10Oe3 07y10Oe3 14y10Oe3 14y10Oe3 45y10Oe5 Oe3 14y10 85y10Oe4 29y10Oe4 29y10Oe3 29y10Oe3 14y10Oe3 66y10Oe3 66y10Oe3 29y10Oe4 07y10Oe3 32y10Oe8 10y10Oe7 335.
36y10Oe3 74y10Oe3 59y10Oe3 04y10Oe3 Oe4 67y10Oe2 Ref This study .
Fig 11.
The several properties of .
different adsorbents towards brilliant green, and .
various adsorbents towards brilliant green and other dyes of different relative molecular mass, (S/N 1-16, and 17-.
in Table 6, respectively Olayinka Oluwaseun Oluwasina et al.
Indones.
Chem.
, 2023, 23 .
, 1077 - 1094
Table 7.
Correlation data of reported and derived adsorption properties of sorbate and sorbents Adsorption All Brilliant green Others Sorbent mass vs.
Moles in solution q vs.
SBET
eSBET vs.
in the solution.
For brilliant green .
%) and other dyes .
45%), the relationship between the moles of sorbent and qp is significant, demonstrating the agreement between the sorptive and the sorbents in this adsorption relationship .
n CONCLUSION This study revealed the successful modification of MGONPs for the adsorption of the cationic brilliant green dye from an aqueous solution.
The following are the conclusions achieved from the study.
the removal of BG was increased by increasing the pH to a maximum pH of 6, then decreased to reach a minimum removal percentage at pH 9.
The pseudo-second-order model best described the experimental adsorption data fitted into the kinetic The adsorption isotherms study revealed that the Freundlich model best-fitted MGONPs.
The maximum adsorption capacity .
for MGONPs was 54.
57 mg gOe1.
A desorption study was carried out, and the SEM-EDX revealed that the dye molecules were desorbed after using acetone as the desorbing agent.
The FTIR analysis showed the disappearance of the characteristic BG dye peaks after the desorption study.
This showed that acetone is an excellent desorbing agent for BG, and the adsorbents can be recovered and recycled for reuse.
Thus, this study indicates that MGONPs is a better adsorbent with higher adsorption capacity for the uptake of BG, and its application in the industry could be further explored.
Additionally, dimensionless preferential adsorption .
and effective surface area .
SBET) performed more accurately than the conventional adsorption capacity and specific surface area (SBET) in providing information about the sorbate-sorbent interface .
We also validated the relevance and accuracy of the new parameters for future adsorption system design by correlation analysis.
Adsorption is, therefore, an excellent method for reducing brilliant green pollutants in an aqueous medium.
Olayinka Oluwaseun Oluwasina et al.
Moles of sorbent vs.
n SBET vs.
eSBET Sorbent mass eSBET q vs.
eSBET
ACKNOWLEDGMENTS
The authors thank the Universitas Airlangga Postdoctoral Fellowship.
Indonesia, for the financial support of this work.
This work was supported by the Universitas Airlangga Postdoctoral Fellowship.
Indonesia (Ref No: 2480/UN3.
22/KS/2.
n AUTHOR CONTRIBUTIONS Olayinka Oluwaseun Oluwasina contributed in Conceptualization.
Visualization.
Investigation.
Olayinka Oluwaseun Oluwasina contributed in Data curation.
Writing- Original draft preparation.
Mochamad Zakki Fahmi contributed in Supervision.
Methodology.
Writing- Reviewing and Editing.
n REFERENCES