Synthesis of nanogeopolymer adsorbent and its application and reusability in the removal of methylene blue from wastewater using response surface methodology (RSM)

Organic dyestuff are mostly toxic compounds that pose serious dangers to the environment. Adsorption using low-cost adsorbents is the most favorable method for its economic aspects. Recently, geopolymers have been introduced as an effective adsorbent for dyes and heavy metals. In this investigation, the synthesis of geopolymers from fired brick waste (Homra) was studied with full characterization using X-ray Diffraction, Fourier Transform Infrared Spectroscopy, Brunauer–Emmett–Teller, Energy dispersive X-ray, Scanning electron microscope tests and Transmission electron microscopy. The synthesized nano-Homra geopolymer (NHGP) was then subjected to the removal of one of the most used basic dyes, Methylene Blue (MB). Adsorption optimization was applied using Response surface methodology to study dye adsorption by the synthesized nano-geopolymer. The independent variables studied were: temperature, contact time, and concentration of dye in the elimination process, which were varied in the range of (25–60 ℃), (10–180 min), and (20–300 mg/L) respectively. The results obtained from ANOVA indicated that the maximum removal efficiency of 95% and adsorption capacity of 80.65 mg/g at a temperature of 59 ℃, contact time of 163 min, and an initial concentration of 254 mg/L. The results showed that the data obtained from the adsorption of MB onto NHGP was compatible with the Pseudo second order (R2 = 0.9838) and Langmuir isotherm model (R2 = 0.9882).


Raw materials
Fired clay brick waste (Homra) was used as a good substitute for the calcined kaolin which is less expensive.The waste was sieved using mesh size 200, the undersize was used in the preparation of the nano geopolymer.Sodium hydroxide and sodium silicate were used as an alkaline activator in the preparation of geopolymer.They were purchased from El Shark El-Awsat company for chemicals, in Cairo, Egypt.The chemical composition and the mineralogical analysis of Homra were determined using the X-ray fluorescence technique (Axios, panalytical 2005, wavelength dispersive sequential spectrometer machine) and X-ray diffraction Brukur D8 advanced computerized apparatus respectively.

Preparation of the geopolymer adsorbent
The aluminum silicates that were present in the Homra waste were mixed with the alkaline activator solution with a solid-liquid (S/L) mass ratio (3/1) using a mechanical mixer to obtain a homogenous mixture.The geopolymer slurry was placed in a cubic iron mold with dimensions (5cm x 5cm).The cubic mold was vibrated using an electric mechanical vibrator to remove any air voids.The sample was kept in the mould for 24 h then de-molded to be cured at room temperature for 28 days.The synthetic geopolymer was crushed and ground to particle size less than100 nm.

Characterization of the adsorbent
The mineralogical analysis was performed on the synthetic geopolymer with X-ray diffraction to determine the crystalline phases (XRD) using BRUKER apparatus for XRD, Axs, D8-ADVANCE (Germany 2001).Brunauer-Emmett-Teller (BET) analysis was used to determine the surface area presence in the synthetic geopolymer and pore size distribution 42 .BET was performed in the presence of nitrogen adsorption-desorption isotherm analysis at a temperature of 77 K using a 3 Flex 3500 microscopic model analyzer.Scanning electron microscope (SEM) analysis was accomplished to determine the prepared adsorbent morphology 43 using JEOL5410 apparatus.The shapes and sizes of the prepared nano-geopolymer were determined using Transmission electron microscopy (TEM) with micro-analyzer electron technique (JEOL JX 1230), while energy dispersive X-ray analysis (EDX) was determined using JEOL JX 2840 apparatus.The main functional group presence in the synthetic geopolymer was determined using Fourier-transform infrared spectroscopy (FT-IR).FT-IR spectrums were recorded on a Jasco FTIR-6100 system, using a pellet made with dehydrated KBr and an instrument in the reflectance mode.The FTIR spectrums were determined between 400 to 4000 cm -1 .

Adsorption experiments
A stock solution of 1g/L was prepared by dissolving (1g) of MB in one liter of double distilled water.The working solutions were prepared by diluting the stock solution with double distilled water to give the required concentration of the working solutions.The hydrogen ion concentration (pH) of the solutions was adjusted using either 0.1N HCl or 0.1N NaOH solutions.The dye concentration was detected by Spectrophotometer (HACH DR 2800) at the maximum wavelength of the dye, λmax = 667 nm.The hydrogen ion concentrations were determined using XS Instrument pH meter.The optimum pH was firstly determined for pH ranging from 2 to 12.
Adsorption can be affected by various factors such as pH, initial concentration of adsorbates, contact time, adsorbent dosage, adsorbent size, and temperature, in addition to agitation speed.The optimization of the above-mentioned factors is essential to maximize outcomes of adsorption, percentage removal, or the adsorption capacity.The adsorption capacity is the predominant.The optimum pH was firstly determined for pH ranging from 2 to 12.The effect of initial conc, time, and temperature were examined according to the principle of Box-Behnken Design.www.nature.com/scientificreports/0.1 g of the synthetic nano-Homra-geopolymer (NHGP) was immersed in 100 mg/L of MB solution at room temperature followed by adjusting pH to 12 then placed in a water bath shaker with a speeding rate of 130 rpm.The experiment procedure is illustrated in Fig. 2. The effect of the initial concentration, time, and temperature were studied.Table 1 shows the conditions of the experimental design.The removal efficiency, R, and the adsorption capacity, q, were determined using the following Eqs.(1 and 2) 44 .where C 0 is the initial concentration of MB solution in (mg/L), C e is the concentration at final time in (mg/L), V is the volume of the solution sample (L), m is the amount of the adsorbent in (g).

Adsorption isotherm, kinetics and thermodynamics of MB
The adsorption isotherm of the MB solution was determined at the optimum conditions using 0.1 g of nano geopolymer adsorbent at different initial concentrations ranging from 20 to 300 mg/L which mainly affects the adsorption capacity.Different adsorption models 45,46 (Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich) were used to identify the most fitted adsorption isotherm model.Langmuir adsorption isotherm assumes the absence of interactions between the adsorbed components, equal energy of sorption, and also homogenous binding sites 47 .Freundlich adsorption isotherm can describe the adsorption for both mono and multilayer 48 .
Temkin adsorption isotherm assumes a linear equation and ignores the low and high concentrations.The uniform distribution of bounding energy was also assumed 45 .Dubinin-Radushkevich (Dub-Rad) isotherm model is used to determine the apparent free energy of the adsorption process and also the characteristic porosity [49][50][51] .
The adsorption isotherm model can be determined according to the following Eqs.( 3) to (7): where C e is the concentration of MB solution at equilibrium in (mg.l -1 ); q e is the adsorption capacity at equilib- rium in (mg.g -1 ); K l is the constant of Langmuir (l.mg -1 ); q m is the maximum theoretical adsorption capacity of the adsorbent in (mg.g -1 ); K f is the constant of Freundlich in (mg (1-n) .L n .g - ); finally n is the adsorption strength constant for Freundlich.B is a Temkin constant (J.mol -1 ) related to the heat of adsorption and is equal to (RT/b), where T is the absolute temperature in (K) and R is a gas constant (8.314J.mol -1 .k - ) while Temkin isotherm constant is expressed by A (L.g -1 ).β is the Dub-Rad constant in (mol 2 /J 2 ), while ε is the Polanyi potential that represents the theoretical adsorption capacity in (J/mol) 52 .
The kinetics of the adsorption process of MB at the optimum conditions using the Pseudo-first order, the Pseudo second order, the Intraparticle, Interparticle diffusion, and Elovich models.Equations (8) to (12) are used to investigate the kinetic model of the adsorption in the linear form 35,[53][54][55][56] .
where q t and q e are the adsorption capacity at any time and equilibrium respectively in (mg/g), t is the time (min) and c is constant (mg.g -1 ).The rate constants for Pseudo-first order, Pseudo-second order, and Intraparticle diffusion are k 1 (min -1 ), k 2 (g.mg -1 .min -1 ) and k p (mg.g -1 .min -0.5 ) respectively.k MD represents the mass transfer diffusion rate constant.α represents the initial absorption rate in (mg.g -1 .min - ), while β is the Elovich constant.
Adsorption thermodynamics was used to identify the energy changes accompanied by the adsorption process.Different parameters were used to check the spontaneous of the adsorption process such as the change of Gibbs (3) Langmuir : 1 ) Pseudo − first order : ln q e − q t = lnq e − k 1 t (9) Pesudo − secondorder : (10) free energy (ΔG, kJ/mol), entropy change (ΔS, kJ/K), and enthalpy change (ΔH, kJ/mol) 24 .These parameters were calculated using the following equations from ( 13) to ( 15) 57,58 .
where C e is the concentration of the liquid phase at equilibrium in (mg/L), q e is the adsorption capacity at equilibrium, R is the universal gas constant, K d is the coefficient of distribution and T is the absolute temperature in Kelvin.

Reusability test of nanogeopolymer
After obtaining the optimal removal efficiency of the adsorbent, a regeneration experiment utilizing a nanogeopolymer adsorbent was conducted.The ideal nano-geopolymer adsorbent, as determined by the experiment, was submerged in a certain pH solution at the optimum conditions.This allowed for three cycles of adsorption tests to ascertain the adsorption stability.After being filtered out, the nano-geopolymer adsorbent was washed five times with methanol (99%) before being dried one last time to remove any last traces of methanol.For every experiment, the MB dye's adsorption capacity and removal efficiency were computed.

Characterization of adsorbent
Mineralogical analysis of nano-geopolymer adsorbent X-ray Diffraction (XRD) is a technique used for determining the atomic and molecular structure of a crystalline material, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions.
XRD has revealed that the main phase present in clay brick waste (Homra) is quartz at 2 ϴ equal to 20.936 and 26.7 as shown in Fig. 3.The firing of the bricks was done below 900 ℃, so the main constituents are quartz and amorphous meta-kaolin.

SEM of NHGP
To inspect the NHGP surface, SEM analysis was investigated.The SEM image with 12,000 × magnification depicted in Fig. 4 shows the formation of the heterogeneous matrix after the polycondensation of raw material.The geopolymer surface was consistent and coarse, with irregular aggregates, as seen in Figure .There were several tiny cavities and holes found with different shapes and sizes in the range of (12-44 nm).This suggests that the geopolymer may operate as an excellent adsorbent.
(13) Aluminosilicates partially dissolve in the alkaline medium, producing an amorphous geopolymer gel along with undissolved particles of crystalline material during the reaction of geopolymerizatio 59 .

Analysis of specific area (BET)
The specific surface area of GP and NHGP were analyzed using BET and the results are illustrated in Table 2.It can be observed that the NHGP has a surface area of 18.36 m 2 /g more than that of GP 11.82 m 2 /g.The high specific surface area of NHGP makes it a good candidate to be used as an adsorbent medium.Generally, the adsorbent's pores are classified into micropores, mesopores, and macropores with diameters less than 2 nm, ranging from 2 to 50 nm and more than 50 nm respectively according to IUPAC regulations 60 .The obtained results show that the produced adsorbent is mesopores type (as discussed in section "TEM analysis of NHGP") which is the most accessible pores to adsorb MB.The prepared geopolymer is an ideal adsorbent that is eco-friendly, non-soluble, mostly efficient, and easy preparation materials.Table 2 shows the BET analysis of the produced adsorbent and different adsorbent from previous studies.
From Fig. 6, it was observed that lower pressure regions show the formation of a monolayer followed by a formation of multilayers.This model is Type IV isotherms with hysteresis loop at a relative pressure till 0.9.BET surface area characterization of NHGP is mesoporous materials, with pore diameters ranging between 2-50 nm giving this type of isotherm.

EDX and FTIR analyses
The chemical analysis of NHGP (EDX analysis) depicted in Fig. 7a contains 25.12 wt% Si, 8.11 wt% Al, and 50.02 wt% O, and there is no sulfur, Cl, or N content in the analysis of NHGP as native adsorbent.It illustrates the composition ratio of Si and Al to be 3.1.
Compared with NHGP after the adsorption of Methylene blue dye chemical analysis, Fig. 7b, which contains mainly 25.36 wt % Si, 7.6 wt% Al, 48.35 wt% O, with the presence of S, Cl, and N which are compatible with the adsorption of MB.
FTIR was used to identify the functional groups involved in the adsorption of MB before and after the adsorption process onto NHGP as shown in Fig. 8.A strong vibration peak centered at 993 cm -1 typical for aluminosilicates can be seen.This peak shifts to 1008 cm -1 with the adsorption of MB.Al-O-Si vibrations correspond to the absorption bands 600-800 cm -1 .The absorption peak of 796 cm -1 was an indication of the presence of quartz 64 .The absorption band around 1443 cm -1 is attributed to stretching vibrations of CO 3 2-ions confirming the existence of carbonate species 65 .The broad band observed at 3255 cm -1 and for geopolymer, is due to the OH and the adsorbed water this peak shifted to 3245 on the adsorption of MB.The stretching bands at 1008.5 cm -1 are for (-NH 2 ) and 1390 cm -1 for (-CH 3 ) that are present in MB that adsorbed onto geopolymer.The peak at 1605 cm -1 is due to asymmetric stretching vibrations of C = O and the peak observed at 1394 cm -1 can be assigned to the aromatic compound group 66 .

Effect of pH on MB adsorption
The adsorption of methylene blue (MB) using NHGP at different pH values is presented in Fig. 9.As demonstrated from the figure, the quantities of MB adsorbed onto the resin were largely raised with the increase in pH, designating that the alkaline environment was more advantageous for MB adsorption.Bearing in mind the cationic nature of MB, electrostatic interactions may occur between MB and the adsorbent surface 67,68 .
Figure 10 illustrates the zeta potential of the geopolymer at different pH's.As a consequence of this data, the zeta potential is negative at the alkaline medium, therefore the surface of NHGP was negatively charged.Thus, electrostatic attraction between MB cations and the adsorbent surface was expected higher pH values.The adsorption of MB onto NHGP is not dependent only on the Electrostatic interactions, as there are some adsorptions that occur at low pH values (Fig. 10).Another mechanism as well as hydrophobic adsorption and electron donor-acceptor (EDA) interactions may affect the adsorption process, this proposed interaction can be seen in Fig. 11 69

ANOVA of MB removal
Table 3 lists the actual and the predicted values of the removal efficiency of MB that was performed according to the designed experiments using Design-Expert v13.The relationship between the different parameters and the removal efficiency of MB was described using multivariate analysis.It was found that the quadratic model was the best fitness function that describes this relation as following Eq.( 16): where Y is the removal efficiency of MB, t is the time of the adsorption, T is the temperature and C is the initial concentration.According to the ANOVA analysis in Table 4, the model is significant and the p-value of lack of fit is 0.3895 which is non-significant (more than 0.05).The values of R 2 and R 2 adj are proportional rises with the significance of the model.Table 5 shows the coefficient of determination of R 2 and R 2 adj equal 0.9915 and 0.9805 respectively for the removal efficiency of MB, while the predicted value of R 2 is 0.9264.Those values show a good agreement between the actual and predicted values presented by the model.
Table 6 shows that all adsorption parameters affect the adsorption performance and removal efficiency of MB.The positive signs for parameters such as time, temperature, and the interaction between time and temperature have a great effect on the adsorption performance, while the negative signs for parameters such as initial concentration and the time square imply that increasing those parameters causes decreasing the performance of the adsorption.
The main diagnostic plots were observed in Fig. 12.The residual of the function model shows a good distribution probability that confirms the assumption accuracy and the independence of the residuals as shown in Fig. 12a.A linear correlation was observed between the predicted and actual values of the experimental data as shown in Fig. 12b while Fig. 12c shows a random distribution of the data points obtained from the experiments with the error line, it was indicated a good prediction and model accuracy.It was observed that the different data of the residuals are in the interval ranges of (4.81963) and (-4.81963) indicating a good prediction of the model as illustrated in Fig. 11d. Figure 12e shows the Pareto graph for the adsorption process that indicates the satisfaction of each variable to the criteria, their values near 1 represent the maximum adsorption reached.The best lambda for the adsorption process was found at 0.63 as illustrated in Fig. 12f the Box-Cox diagram which indicates that the data was suitable and didn't need any improvement 44,50 .sites and adsorbents.This behavior is due to the rapid diffusion of the MB dye molecules from the synthetic wastewater to reach the active sites present in the NHGP 72 which indicates that a higher temperature is preferred for the adsorption process.Figure 13d-f show the effect of contact time and adsorption temperatures at initial concentrations ranging from 20 to 300 ppm on the removal efficiency of MB.It can be understood that the effect of the adsorption time is more dominant than the effect of the adsorption temperature.It can be observed that the maximum removal efficiency of MB at a temperature of 60 ℃, a time of 180 min ranging from 80 to 100% at initial concentrations of 20 ppm and 300 ppm respectively.The reason for this behavior is that the high initial concentration of MB causes a high concentration gradient leading to the high driving force for the transfer of the molecules quickly to the active sites 73 .It was observed that increasing the initial concentration of MB causes increasing the loading capacity of NHGP adsorbent that complies with the results obtained from the adsorption of MB using green olive stones 66 .

Effect of interactive different parameters on adsorption removal efficiency of MB
Finally, Fig. 13g-i show the relationship between the adsorption temperature and initial concentrations at different contact times ranging from 10 to 180 min on the removal efficiency.It can be observed that the effect of the adsorption temperature is more dominant than the initial concentration and also increasing the contact time between the adsorbent and the MB solution causes increasing in the removal efficiency due to allowing a sufficient time to adsorb MB on the NHGP.Adsorption capacity increases as the contact time increases to a point, after which further increase in the contact time does not increase adsorbate uptake on adsorbent due to saturation and there will be no significant change in the removal efficiency of MB 74 .

Optimization of MB removal efficiency
The optimum removal efficiency of MB was obtained from the program software using the optimization tab.The constraints of each parameter were set as illustrated in Table 7.The optimal parameters were found to be at a temperature of 59 ℃, initial concentration of MB of 254 ppm, and adsorption time of 163.2 min to obtain a predicted value for removal efficiency of MB of 95% with the desirability of 1 as illustrated in Table 8.To validate these results the suggested optimum parameters were performed five times at the optimum conditions to calculate the mean removal efficiency of MB of 94.4% with a standard deviation of 1.4% with an error percentage of 0.63 which proves the validity of the model.

Isotherm models of the adsorption of MB onto NHGP
Studying the Langmuir isotherm model, it has been stated that the adsorbent surface is homogeneously distributed having identical adsorbent sites and there is no lateral interaction forming a monolayer.From Fig. 14a it was found that the correlation coefficient of the model (R 2 ) is equal to 0.988 which indicates that the adsorption of MB with NHGP is well fitted with this model with a maximum capacity of 80.65 mg/g.Figure 14b represents the fitting of the isotherm data with the linear form of the Freundlish model.The Freundlich adsorption isotherm model is used to describe heterogeneous systems.From the fitting data and the correlation factor (R 2 = 0.9418), we deduced that this system is moderately fitted with the Freundlish model.
The 1/n value obtained from the Freundlich isotherm plot is 0.6036 which falls between 0 and 1 indicating the adsorption is linear and uniform throughout the surface.According to the 1/n value (0 < 1/n < 1), this isotherm is a favorable physical process.
The Temkin model in Fig. 14c clarifies the variation in the heat of adsorption and the interactions of adsorbate-adsorbate molecules during the progression of the adsorbed layer.The correlation coefficient of this model is 0.8846 which indicates poor fitting for the adsorption of MB with NHGP. Figure 14d shows the Dub-Rad model that is suitable for moderate concentration of the adsorbate and assumes multilayer properties as Vander Waals  www.nature.com/scientificreports/forces are involved and the physical adsorption process can be applied 75 .Table 9 shows the fitting parameter of the four adsorption isotherm models.

Kinetics of the adsorption of MB onto NHGP
Figure 15a illustrates the adsorption capacity and the rate of the adsorption of MB onto the NHGP.It can be observed there is rapid adsorption takes place at a time ranging from 0 to 45 min to increase the adsorption capacity from 0 mg/g to 31.57mg/g respectively.The removal efficiency of MB is enhanced as the contact time  Kinetics of MB adsorption on NHGP were determined using Pseudo first order, Pseudo second order, Intraparticle diffusion, Interparticle diffusion, and Elovich models as illustrated in Fig. 15b-f to identify the best-fitted model and analyze the MB adsorption process.Table 10 shows the fitting parameters for the five kinetic adsorption models, which designated that the Pseudo Second Order kinetic model is the most applicable model for this process.It has a correlation coefficient of (R 2 = 0.9838) which is higher than the four other models.According to this model, it was found that the equilibrium adsorption capacity and adsorption rate constant were 28.41 mg.g -1 and 9.14 × 10 -3 g. mg -1 .min - respectively.Choosing of Pseudo Second Order model is considered the most suitable model for the adsorption process.It is also indicated that the adsorption is a chemisorption type and the adsorption rate doesn't depend on the adsorbate concentration but depends on the adsorption capacity 76 confirmed by the results obtained from the Design-Expert software.

Adsorption thermodynamics
Thermodynamic parameters were assessed for the removal of MB dye by using NHGP synthesized adsorbent in the temperature range of 25 to 60 ℃. Figure 16 illustrates the calculations of the thermodynamics variables ΔS° and ΔH°.The K d values were obtained from the adsorption data at different temperatures.The ΔG° values shown in Table 11 confirm that the adsorption process was spontaneous at the selected temperature range (25-60 ℃), which is in concurrence with the ΔS° value (ΔS > 0 for the spontaneous process).The calculated value of ΔH° (+ ve 79.9 kJ/mol) is implicit in the endothermic characteristics of the process.
Moreover, the adsorption process may be classified as a chemical process or, a physical process, or may be operated by the two mechanisms simultaneously 77 .The ΔH value for van Edward force, hydrogen bond, ligand exchange, dipole interaction, and chemical bond is 4-10, 2-40, ≈ 40, 2-29, and > 60 kJ⋅mol -1 , respectively 78 .The ΔH value of the adsorption of MB onto synthesized NHGP was 79.7 kJ.mol -1 , indicating the adsorption by a chemical bond.
The adsorption capacity of NHGP synthesized in the current study for methylene blue is compared with the adsorption capacity of different composite geopolymers as shown in Table 12.According to the data below, it can be indicated that the NHGP produced from fired brick waste (Homra) is a suitable sorbent for MB removal from economic and environmental perspectives.

Desorption and reusability for MB adsorption
The commonly employed alcohol-washing method was first used for the regeneration of NHGP.During alcohol washing, the color of the solution turned from transparent to blue, indicating the desorption of MB from the spent adsorbent.After three times washing, the regenerated NHGP was used for the next adsorption run.As shown in Fig. 17, qe of MB decreased sharply in the next adsorption runs.The decreased amount of adsorption was attributed to residual MB on the surface of NHGP.As discussed in the "Effect of pH" section, although electrostatic repulsion existed between MB and the adsorbent surface at lower pH values, hydrophobic adsorption, and electron donor-acceptor (EDA) interaction could still lead to the adsorption of MB.In other words, the adsorbed MB could not completely desorb in the regeneration process, and also 20% of the adsorbent weight was lost during the regeneration.In addition, although repeated washing could enhance the desorption of MB, more spent washing alcohol and water would be produced, which needs further treatment.Thus, the regeneration method was not favorable from a practical viewpoint that decreased the removal efficiency from 95% at the first use to 70% at the second use and finally to 42%.

Conclusion
This work effectively synthesized a nano-geopolymer from waste-fired brick (Homra) as a novel solid particle adsorbent for wastewater purification, offering an unanticipated opportunity to control the geopolymer materials' structure for high-efficiency dye adsorption.The nano geopolymer was prepared using a 12M NaOH solution as an activator, with a 3:1 Na 2 SiO 3 /NaOH ratio.The nano-Homra geopolymer (NHGP) ideal SBET-specific surface area was 18.3658 m 2 /g, which offered enough channels for the mass transfer and adsorption processes.At the optimal conditions of 59 ℃ temperature, 254 mg/L initial concentration, and 163 min experiment duration, the novel nano-geopolymer adsorbent particles demonstrated high adsorption efficiency for MB dye, with a maximum adsorption capacity reaching 80.65 mg/g with a removal efficiency of 95.11%.Additionally, the test findings also demonstrated that the main external constraints affecting the entire adsorption process were the adsorbent concentration and experiment time.Additionally, the adsorbent's regeneration removal effectiveness was tested without causing a significant mass loss.The modified matrix structure of the nano-geopolymer was associated with the enhanced porosity and adsorption characteristics of the adsorbent.Because of their straightforward construction and practical treatment method, the resulting adsorbents were the predominant substitutes for more expensive or powder adsorbents.The novel nano-geopolymers have the potential to be used as adsorbent or carrier materials in various industrial applications.
Box-Behnken design (BBD) is used to design and optimize the main parameters affecting the removal efficiency of the MB solution using Design-Expert version 13 software.Three variables were used in the design of the experiments: adsorption time (10-180 min), adsorption temperature (25-60 ℃), and initial concentration of the MB (20-300 mg/L) while keeping the adsorbent dose fixed during the experiments (0.1 g).The removal efficiency of the MB solution was used as a response value of the experimental design.

Run A :
Time min B: Temperature ℃ C: Initial Conc mg/L
Figure 13a-c show the relationship between the time, initial concentrations of MB at different adsorption temperatures (25 ℃, 42.5 ℃, and 60 ℃), and the adsorption removal efficiency of MB.It can be observed that increasing the temperature causes increasing in the removal efficiency of MB at different initial concentrations and times.Temperature affects the adsorption process based on the type of bonds formed between adsorbate (16) Y = 48.61731+ 0.144115t − 0.493188T − 0.298732C + 0.007188tT + 0.000346tC + 0.005838TC − 0.001421t 2 − 0.000306T 2 − 0.000068C 2

Figure 8 .
Figure 8. FTIR Analysis of Geopolymer before and after Adsorption.

Figure 9 .
Figure 9. Influence of pH on the Adsorption Capacity of MB Dye onto NHGP.

Figure 10 .
Figure 10.Zeta Potential of NHGP at Different pH.

Figure 11 .
Figure 11.Schematic Diagram for the Proposed Reaction between MB and NHGP.

Figure 13 .
Figure 13.3D Response Surface Plots of for the Effect of Different Parameters on the Adsorption Removal Efficiency of MB.

Table 1 .
Experimental Condition of Removal Efficiency of MB Using Design Expert.

Table 3 .
Experimental Conditions of Actual and Predicted Values of Removal Efficiency of MB from Wastewater.

Table 4 .
ANOVA Analysis of the Removal Efficiency of MB from Wastewater.
SourceSum of squares df Mean Square F-value p-value

Table 5 .
Statistics fit model.increasestill reaches 45 min, then at times ranging from 45 to 120 min the adsorption capacity was nearly unchanged ranging from 31.57mg/g to 28.44 mg/g due to reaching equilibrium.

Table 8 .
Results of the Optimum Solutions.

Table 9 .
Isotherm Models Parameters of the Removal of MB by NHGP.

Table 10 .
Kinetics Parameters of MB Adsorption onto NHGP.Figure 16.Linear Relationship of Van't Hoff Equation at Different Adsorption Temperatures.

Table 11 .
Thermodynamic Parameters of the removal of MB Dye by using NHGP.

Table 12 .
Comparison between Different Geopolymer Adsorbents for MB Adsorption Uptake.