Ionic liquid-modified magnetic graphene oxide nanocomposite as a powerful adsorbent for the removal of lead ions and brilliant blue dye

doi:10.21203/rs.3.rs-4986593/v1

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Ionic liquid-modified magnetic graphene oxide nanocomposite as a powerful adsorbent for the removal of lead ions and brilliant blue dye

https://doi.org/10.21203/rs.3.rs-4986593/v1

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In this research, a magnetic graphene oxide modified with ionic liquid has been synthesized and used as a powerful nanocomposite for the removal of lead (Pb²⁺) ions and brilliant blue (BB) dye from a water sample. This nanocomposite was characterized by using EDS, FTIR, SEM, and VSM techniques, which confirmed the successful formation of the desired nanocomposite and good immobilization of the ionic liquid. The ultraviolet-visible (UV-Vis) and atomic absorption (AA) spectroscopy techniques were employed to quantify the extent of removal of Pb²⁺ ions and BB dye. The removal percentages of Pb²⁺ ions and BB dye by the prepared nanocomposite were 94% and 96%, respectively, demonstrating its excellent performance. According to the Langmuir isotherm, the maximum adsorption capacities of the nanocomposite toward Pb²⁺ ions and BB dye were achieved to be 83.34 and 84.76 mg g^− 1, respectively. Also, this nanocomposite was recoverable and reusable at least three times.

Earth and environmental sciences/Environmental sciences

Physical sciences/Chemistry

Magnetic graphene oxide

Ionic liquid

Adsorbent

Lead ions

Brilliant blue dye

Water, the most abundant molecule on earth, plays an important role in supporting the survival of a wide range of living organisms. Its absence would jeopardize a multitude of essential functions that are vital for life. Water pollution, which stems from the discharge of chemical, mineral, biological, and research materials from industrial plants, factories, and hospitals, is a significant environmental challenge for chemists ^1–8. Contaminated water poses serious threats and inflicts detrimental effects on the health of humans, animals, ecosystems, and plants ^9–11. These types of water pollution contain pollutants such as heavy metals, dyes, and organic and inorganic substances soluble in water, as well as pathogens. Numerous sources contribute to heavy metal and dye pollution, including mining activities, smelting, battery production, leather tanning, oil refining, dye production, pesticide application, pigment manufacturing, and printing and photography industries. Pollutants containing toxic metals like Cd, Hg, Ag, and Pb, as well as anionic and cationic dyes, pose significant health risks, including brain damage, kidney diseases, cancer, and systemic disorders ^{2, 12–16}. To remove pollutants such as metals and toxic dyes, a variety of methods are employed, including absorption, flocculation, ultrafiltration, biodegradation, reverse osmosis, sedimentation, ion exchange, electrodes, membrane separation, and photocatalysis. Among these, is a highly effective method for removing pollutants from water and air, offering numerous advantages of simplicity, cost-effectiveness, environmental compatibility, and lack of harmful byproducts. Pollutants are removed from air or water by adhering to the surface of a solid material through physical and chemical interactions ^{12, 13, 17–19}. Activated carbon, zeolites, alumina oxides, silica gels, and other materials are employed as adsorbents in the surface adsorption method ^20–23. A suitable adsorbent should possess characteristics of non-toxicity, biodegradability, economic viability, and high efficiency, making carbon compounds and allotropes excellent candidates for this purpose ^24–27. Among the most significant and versatile allotropes of carbon is graphene oxide (two-dimensional), where carbon atoms exhibit sp² (honeycomb) hybridization, and its surface is replete with hydroxy, carboxylic acid, and epoxy functional groups. The remarkable properties of graphene oxide include exceptional strength, superior electrical and thermal conductivity, remarkable heat capacity, an extensive surface-to-volume ratio, extraordinary catalytic potential, and exceptional flexibility. Graphene oxide finds application in diverse fields, including water treatment, pharmaceutical carriers, hydrogen storage, high-performance filters, coating medical devices, biosensors, reinforcing structures and composites, catalysts, and adsorbents ^28–31. Given the remarkable properties discussed above, graphene oxide emerges as a promising adsorbent for removing dyes, paints, and heavy metals, offering an environmentally friendly solution for pollutant treatment. However, one of the challenges associated with utilizing graphene oxide as an adsorbent is the difficulty in separating it from the operating environment. This issue can be effectively addressed by introducing magnetic to the adsorbent’s surface ^32–35. Iron oxide is one of the most important magnetic oxides that finds extensive use due to its abundance, exceptional surface-to-volume ratio, minimal toxicity, and convenient separation using external magnets ^36–39. Furthermore, to enhance the adsorption capacity of magnetic graphene oxide, their surface can be modified by novel green materials such as ionic liquids. Ionic liquids are environmentally friendly compounds composed of two anions and cations, where the cation is organic or inorganic. These Ionic compounds are well-suited for applications as solvents, adsorbing, and catalysts due to their inherent low vapor pressure and exceptional chemical and thermal stability ^40–45. In view of the above here, and novel ionic liquid converter magnetic graphene oxide nanocomposite (GO@Fe₃O₄@SiO₂-NH₂/IL) prepared, characterized, and applied as an efficiency and green nanocomposite for the adsorption and removal of Pb²⁺ ion and also BB dye from wastewater.

2.1. Production of GO@Fe₃O₄@SiO₂-NH₂

The GO@Fe₃O₄@SiO₂-NH₂ nanocomposite was prepared through the following steps. First, 0.6 g of GO was thoroughly dispersed in 25 mL of distilled water for approximately 20 min. Next, 0.3 g of Fe₃O₄@SiO₂-NH₂ was added and the obtained combination was stirred vigorously at 70°C for 2.5 h. Ultimately, by using a magnet the product was separated, washed with EtOH and H₂O, dried at 65°C for 7 h, and called GO@Fe₃O₄@SiO₂-NH₂ ⁴⁶.

2.2. Production of GO@Fe₃O₄@SiO₂-NH₂/IL

To synthesize GO@Fe₃O₄@SiO₂-NH₂/IL, 0.5 g of GO@Fe₃O₄@SiO₂-NH₂ was first dispersed in dry toluene (30 mL). Subsequently, 0.2 mmol of IL was added to the reaction vessel and this was refluxed for 24 h. By using a magnet, the product was separated, washed with EtOH, dried at 65°C for 7 h, and called GO@Fe₃O₄@SiO₂-NH₂/IL⁴⁷.

2.3. Batch adsorption experiments

The absorption test was carried out in glass vials containing synthesized adsorbents (0.005, 0.01, 0.015, and 0.02 g) and pollutant concentration (Pb²⁺ ion and BB dye) in the range of 5 mg/L to 30 mg/L. The vials were continuously stirred using a stirrer for 15 to 45 minutes at different temperatures of 25°C, 45°C, and 70°C. HCl and NaOH were used to adjust the pH of the solution. Moreover, different amounts of adsorbent were added to 50 mL of BB dye and 30 mL of Pb(NO₃)₂ solution to achieve the desired concentrations. By dissolving 0.016 g Pb(NO₃)₂ in 100 mL of distilled water, the corresponding standard solution was obtained. Also, by dissolving 0.01 g BB in distilled water (100 mL), the standard solution of BB was prepared.

After the desired time for pollutant absorption by the designed GO@Fe₃O₄@SiO₂-NH₂/IL nanocatalyst, this adsorbent was removed by using a magnet. The filtered solution was then analyzed using atomic absorption spectroscopy (AAS) and UV-Vis spectroscopy to determine the concentration of the remaining pollutants. The removal percentage of Pb²⁺ ion and BB dye was calculated using the following formula:

Pb²⁺ or BB dye removal percentage = [(C₀ - C_t)/C₀] × 100

where C₀ (mg L^− 1) is the primary concentration of pollutants (Pb²⁺ ions and BB dye) in an aqueous solution and C_t (mg L^− 1) is the residual concentration of them at time t.

3.1. Preparation and characterization of the GO@Fe₃O₄@SiO₂-NH₂/IL adsorbent

For the preparation of this nanocomposite, firstly, Fe₃O₄@SiO₂-NH₂ was prepared according to our previous procedure ⁴⁷. Then, GO was composted with Fe₃O₄@SiO_₂-NH₂ to give GO@Fe₃O₄@SiO₂-NH₂. Next, the latter magnetic material was chemically modified with ionic liquid (IL) to deliver the GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite (Fig. 1).

This composite was characterized by using FT-IR, SEM, VSM, EDS mapping, and EDS elemental analyses. FT-IR of prepared composites are shown in Fig. 2. For all materials, the sharp peaks in the region of 3400–3425 cm^− 1 are due to O-H and N-H bonds (Figure. 2b and 2c). The peak appearing at 2945 cm^− 1 is for aliphatic C-H bonds (Figures. 2b and 2c) ^{48, 49}. The observed peaks at 1750, 1626, and 1540 cm^− 1 are respectively related to the carboxyl (C = O) groups of GO, the C = N and C = C bonds of ionic liquid (Figures. 2a-2c). The peak at 1100 cm^− 1 corresponds to the epoxy C-O and alkoxy C-O bonds of GO (Figures. 2a-2c) ⁵⁰. The peak at 550 cm^− 1 is assigned to the Fe-O bond. Also, the signals at 870 and 1110 cm^− 1 are due to the Si-O-Si bonds of the silica shell (Figures. 2b and 2c) ^{51, 52}. These results confirm the high stability and successful immobilization of silica and ionic liquid species onto the material surface.

The SEM image of the GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite provides a clear view of the dispersed spherical iron oxide nanoparticles on the folded graphene oxide layer Fig. 3.

Vibrating sample magnetometer (VSM) analysis of the Fe₃O₄ and GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposites was also performed and the result is shown in Fig. 4. According to this analysis, the magnetization of the Fe₃O₄ and GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposites were, respectively, found to be 63 and 21 emu/g which confirms the successful chemical stabilization of GO moieties on Fe₃O₄.

The TGA curve of GO@Fe₃O₄@SiO₂-NH₂/IL cleared two weight losses. At temperatures in the range of 25 to 130°C, a weight loss of about 0.64% is assigned to the removal of water and organic solvents. The main weight loss at 210–580°C (about 31%) corresponds to the elimination of grafted IL moieties confirming the high stability and well immobilization of IL species on the material surface Fig. 5.

The PXRD of GO@Fe₃O₄@SiO₂-NH₂/IL showed a pattern with six reflection peaks at 2θ of 32, 38, 42, 58, 63 and 68 degrees, corresponding to the Miller indices values (hkl) of 440, 511, 422, 400, 311 and 220, respectively, proving that the crystalline structure of the magnetite NPs is maintained during the adsorbent preparation steps Fig. 6 ⁵³.

The EDS and EDS mapping analyses showed the presence and well distribution of C, N, Si, Fe, and O elements onto/into the nanocomposite framework and also confirmed the successful immobilization of the ionic liquids on the surface of the nanocomposite Figs. 7 and 8.

3.2. Adsorption studies

3.2.1. Effect of pH

In the adsorption of Pb²⁺ and BB dye by GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite, the pH effect was investigated. For this content, the pH was changed from 4 to 10, while other effective parameters including temperature (25°C), sonication time (20 min), initial concentration (Pb²⁺ and BB) (10 mgL^− 1), and the adsorbent dose (0.01 g) were kept constant. According to the results of Fig. 9a, pH = 7 was found to be the optimal pH for the removal of both Pb²⁺ and BB. The decrease in removal percentage under acidic conditions can be attributed to the overabundance of H⁺ ions, which can compete with BB dye and Pb²⁺ ions ³. In addition, under acidic conditions, the adsorbent surface receives a positive charge, causing a strong electrostatic repulsion between the adsorbent and Pb²⁺ ions, thereby reducing the removal percentage. Furthermore, at alkaline pH (pH > 7), Pb²⁺ ions precipitate, which reduces their removal. At alkaline pH (pH > 7), the adsorbent surface becomes negatively charged creating a strong electrostatic repulsion with the BB dye.

3.2.2. Temperature effect

The temperature effect (25, 30, 45, and 70°C) on the adsorption of Pb²⁺ ions and BB dye molecules was evaluated at the fixed values of other parameters (0.01 g of the adsorbent, initial concentration of Pb²⁺ and BB (10 mg L^− 1), pH 7 and sonication time of 20 minutes). This showed that with increasing the temperature, the adsorption of both BB and Pb²⁺ is increased. As shown in Fig. 9b, the highest adsorption of BB (97%) is achieved at 45°C., while in comparison, the highest adsorption of Pb²⁺ (95%) is obtained at 70°C.

3.2.3. Contact time effect

The contact time effect (15–45 minutes) on the removal of Pb²⁺ ions and BB dye by GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite was investigated. The other parameters, including temperature (70°C for Pb²⁺ ions, 45°C for BB dye, pH = 7, initial concentration of Pb²⁺ (10 mg L^− 1), initial concentration of BB dye (10 mg L^− 1) and adsorbent amount (0.01 g) were kept constant. As can be seen from Fig. 9c, with increasing the contact time, the removal percentage of both Pb²⁺ ions and BB dye molecules is increased. This is because the increase in the contact time increases the interactions between pollutants and the adsorbent and, subsequently, enhances the removal percentage. The maximum removal of Pb²⁺ ions and BB dye molecules was achieved in a contact time of 35 minutes. After 35 minutes, the removal efficiency was decreased, which may be attributed to the desorption of Pb²⁺ ions and BB dye molecules under ultrasonic irradiation.

3.2.4. Adsorbent dose effect

To evaluate the adsorbent amount effect on the removal of Pb²⁺ ions and BB dye molecules by GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite, different doses of adsorbent (0.005, 0.01, 0.015, and 0.02 g) were evaluated under the optimum values of the other parameters. The values of other parameters were: contact time (35 minutes), temperature of 45°C for BB molecules and 70°C for Pb²⁺ ions, initial concentration of 10 mg L^− 1 for Pb²⁺ and BB molecules, and pH = 7. According to the data presented in Fig. 9d, by increasing the adsorbent amount from 0.005 g to 0.015 g, the removal percentage was increased. This is because increasing the adsorbent amount increases the interaction sites for adsorbing pollutants. As shown, the maximum adsorption of Pb²⁺ ions and BB molecules is achieved using only 0.015 g of the nanocomposite.

3.2.5. Effect of the initial concentrations of Pb²⁺ ions and BB dye molecules

The effect of the initial concentrations of Pb²⁺ ions and BB dye molecules (5–30 mg. L^− 1) on the removal process by the GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite was also examined. The values of the other parameters were: adsorbent dose of (0.015 g), temperature (45°C for BB and 70°C for Pb²⁺), sonication time (25–35 minutes), and pH = 7. According to the findings of Fig. 9e, the removal percentage of BB dye and Pb²⁺ ions was decreased by increasing their initial concentrations. At lower concentrations of Pb²⁺ and BB, the GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite sites have more opportunities to interact with Pb²⁺ ions and BB dye molecules. By increasing concentrations of Pb²⁺ and BB, the adsorption sites of the nanocomposite are saturated, and then the removal percentage is decremented.

Next, the EDS analysis was carried out to evaluate the efficiency of the GO@Fe₃O₄@SiO₂-NH₂/IL adsorbent for the removal of Pb ion and BB dye. After adsorption process, the new signals of Pb and S have been observed in the EDS spectra (Figs. 10 and 11), confirming the successful removal of both Pb ions and BB dye on the designed GO@Fe₃O₄@SiO₂-NH₂/IL adsorbent.

3.3. Adsorption isotherms

To properly understand the adsorption mechanism, as well as the maximum adsorption of BB and Pb^+ 2 by GO@Fe₃O4@SiO₂-NH₂/IL, different isotherm models, including Langmuir, Freundlich, and Temkin, were assessed ^{47–50, 54, 55}. The results are presented in Table 1.

Table 1

Adsorption isotherm models parameters for the adsorption of Pb^+ 2 and BB using GO@Fe₃O₄@SiO₂-NH₂/IL
BB Pb Adsorbent dosage (g) 0.01 0.015
Isotherm Parameters Value of parameters
Langmuir	Q_m (mg g^_1) K_a (L mg^_1) R²	84.76 68 0.952	83.34 98 0.939
Freundlich	1/n K_F (L mg^_1) R²	0.245 2.25 0.940	0.340 4.23 0.937
Temkin	B1 K_T(L mg^_1) R²	16.91 5.84 0.950	12.83 8.73 0.909

The equations of the isotherms are as follows:

Langmuir\(\frac{\varvec{C}}{\varvec{q}}\varvec{=}\frac{\varvec{1}}{{\varvec{K}{\varvec{q}_\varvec{m}}}}\varvec{+}\frac{\varvec{C}}{{{\varvec{q}_\varvec{m}}}}\):

In this relation, C (mg L^− 1) represents the concentration of equilibrium of the species (the remaining concentration of the species in the solution that the adsorbent could not absorb), q (mg g ^− 1) is the amount of species absorbed on the surface of the adsorbent, K (L mg ^− 1) is Langmuir's equilibrium constant, and q_m (mg. g ^− 1) is the maximum amount of species that can be absorbed by a certain amount of adsorbent ^{51, 52}.

Freundlich:

\(\varvec{Ln}{\varvec{q}_\varvec{e}}\varvec{=Ln}{\varvec{K}_\varvec{f}}\varvec{+}\frac{\varvec{1}}{\varvec{n}}\varvec{Ln}{\varvec{C}_\varvec{e}}\)

where q_e (mg/g) is the amount of substance absorbed per adsorbent mass, and C_e (mg/L) is the concentration of the equilibrium in the solution. Freundlich's constants, n and K_f, are the adsorption intensity and relative adsorption capacity of the adsorbent, respectively. When K_f increases, the adsorption capacity of the adsorbent increases to absorb the adsorbed substance ^{52, 56}.

Temkin:

\({\varvec{q}_\varvec{e}}\varvec{=}{\varvec{B}_\varvec{1}}\varvec{Ln}{\varvec{K}_\varvec{t}}\varvec{+}{\varvec{B}_\varvec{1}}\varvec{Ln}{\varvec{C}_\varvec{e}}\)

B₁ and K_t are the parameters of the model, which are calculated by using the chart that B = RT/b and K_t are the temperature constants of Temkin, which are proportional to the heat of surface adsorption and the bond constant associated with the maximum bond energy. The adsorption isotherm diagrams of BB and Pb^+ 2 (Langmuir, Freundlich, and Temkin), are shown in Table 1. According to the results of Table 1, the removal process was followed by the Langmuir and Freundlich models, which was due to their higher R² compared to the Temkin. The Langmuir model undertakes that the process of adsorption is monolayer and the surface of the adsorbent is homogenous. While the Freundlich model undertakes that this process is multilayer and the surface of the adsorbent is heterogeneous. The maximum adsorption according to the Langmuir model for BB dye molecules and Pb^+ 2 ions were 84.76 and 83.34 mg g^− 1, respectively. The n values of the Freundlich model were greater than 1, which represents a promising adsorption condition. The n values between 2–10 in the model of Freundlich show an easy adsorption. Moreover, the n = 1–2 and n < 1 illustrate moderate and difficult adsorption, respectively.

3.4. Possible mechanism of absorption

The adsorption mechanism of Pb^+ 2 and BB by GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite was investigated. Since the GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite contains the ionic liquid ion pairs, therefore, the adsorption of both BB cationic dye and Pb²⁺ ions may be performed via their electrostatic interaction with the ionic liquid moieties Fig. 12.

The recyclability and reusability of GO@Fe₃O₄@SiO₂-NH₂/IL nanocomposite were also studied in the adsorption of both Pb^+ 2 and BB under optimal conditions. For this purpose, after the completion of the adsorption process for each sample, the absorbent was magnetically separated and washed completely with water and ethanol. Then, it was reused under the same conditions as the first run. It was found that the designed adsorbent could be recovered and reapplied at least three times with no significant loss of efficiency Fig. 13. These results confirm the high performance and excellent stability of the designed adsorbent in practical conditions.

In this research, a novel magnetic nanocomposite (GO@Fe₃O₄@SiO₂-NH₂/IL) was developed to remove Pb²⁺ ions and BB dye from aqueous solutions. This nanocomposite was characterized by using FT-IR, EDX, SEM, TG, and VSM analyses. The effects of initial concentration, pH value, initial concentration of pollutant (Pb²⁺ ions or BB dye), time, and adsorbent amount on the adsorption of Pb²⁺ ions and BB dye by GO@Fe₃O₄@SiO₂-NH₂/IL were studied to determine the optimal conditions. The findings revealed that the optimal conditions were achieved at pH 7, 0.01 g of adsorbent, 5 min of contact time, and initial pollutant concentrations of 5 mg L^− 1 and temperatures of 45°C for BB dye and at 70°C for Pb²⁺ ions. The ease of separation of the nanocomposite using an external magnet, rapid adsorption rate, ability to recycle up to four times with minimal waste, superior adsorption capacity for heavy metals and dye pollutants, and environmentally friendly nature of the adsorbent stand out as its unique and superior characteristics compared to other previously developed adsorbents.

Competing interests

The authors declare no competing interests.

Author Contribution

F. D.: Investigation, Writing—original draft, Formal analysis, Resources. D. E.: Conceptualization, Writing – review& editing, Visualization, Supervision.

Acknowledgements

The authors thank Yasouj University and Iran National Science Foundation (INSF) for supporting this work.

Data Availability

All the research date is include in the manuscript.

F.S. Abdulraheem, Z.S. Al-Khafaji, K.S. Hashim, M. Muradov, P. Kot, A.A. Shubbar, in Natural filtration unit for removal of heavy metals from water, p. 012034, IOP Publishing, Abdulraheem, F. S., Al-Khafaji, Z. S., Hashim, K. S., Muradov, M., Kot, P., & Shubbar, A. A. Natural filtration unit for removal of heavy metals from water. Mater. Sci. Eng. A 888, 1, p. 012034 (2020) (2020).
Kishor, R., Purchase, D., Saratale, G. D., Saratale, R. G., Ferreira, L. F. R., Bilal, M., ... & Bharagava, R. N. Ecotoxicological and health concerns of persistent coloring pollutants of textile industry wastewater and treatment approaches for environmental safety. J. Environ. Chem. Eng 9, 105012 (2021).
Pahl-Wostl, C., Vörösmarty, C., Bhaduri, A., Bogardi, J., Rockström, J., & Alcamo, J. Towards a sustainable water future: shaping the next decade of global water research. Curr. Opin. Environ. Sustain., 5, 708-714 (2013).
Hanafi, M. F., & Sapawe, N. A review on the water problem associate with organic pollutants derived from phenol, methyl orange, and remazol brilliant blue dyes. Mater. Today: Proc 31, A141-A150 (2020).
Carolin, C. F., Kumar, P. S., Saravanan, A., Joshiba, G. J., & Naushad, M. Efficient techniques for the removal of toxic heavy metals from aquatic environment: A review. J. Environ. Chem. Eng 5, 2782-2799 (2017).
Hlihor, R. M., & Gavrilescu, M. (2009). Removal of some environmentally relevant heavy metals using low-cost natural sorbents. Environ. Eng. Manag. J 8, 2 (2009).
Byrne, C., Subramanian, G., & Pillai, S. C. Recent advances in photocatalysis for environmental applications. J. Environ. Chem. Eng 6, 3531-3555 (2018).
Matatov-Meytal, Y. I., & Sheintuch, M. Catalytic abatement of water pollutants. Ind. Eng. Chem. Res 37, 309-326 (1998).
Zhao, M., Xu, Y., Zhang, C., Rong, H., & Zeng, G. New trends in removing heavy metals from wastewater. Appl. Microbiol. Biotechnol 100, 6509-6518 (2016).
Chen, W., Lu, Z., Xiao, B., Gu, P., Yao, W., Xing, J., ... & Wang, S. Enhanced removal of lead ions from aqueous solution by iron oxide nanomaterials with cobalt and nickel doping. J. Clean. Prod 211, 1250-1258.
Robati, D. Pseudo-second-order kinetic equations for modeling adsorption systems for removal of lead ions using multi-walled carbon nanotube. J. Nanostructure Chem 3, 1-6 (2013).
Saravanan, A., Kumar, P. S., Jeevanantham, S., Karishma, S., Tajsabreen, B., Yaashikaa, P. R., & Reshma, B. Effective water/wastewater treatment methodologies for toxic pollutants removal: Processes and applications towards sustainable development. Chemosphere 280, 130595 (2021).
Elgarahy, A. M., Elwakeel, K. Z., Mohammad, S. H., & Elshoubaky, G. A. A critical review of biosorption of dyes, heavy metals and metalloids from wastewater as an efficient and green process. Clean. Eng. Technol 4, 100209 (2021).
Tahir, M. B., Nawaz, T., Nabi, G., Sagir, M., Khan, M. I., & Malik, N. Role of nanophotocatalysts for the treatment of hazardous organic and inorganic pollutants in wastewater. J. Environ. Anal. Chem 102, 491-515 (2022).
Tangahu, B. V., Abdullah, S. R. S., Basri, H., Idris, M., Anuar, N., & Mukhlisin, M. Isolation and screening of rhizobacteria from Scirpus grossus plant after lead (Pb) exposure. J. Civ. Eng. Archit 5, 484-493 (2011).
Ali, H., Khan, E., & Ilahi, I. Environmental chemistry and ecotoxicology of hazardous heavy metals: environmental persistence, toxicity, and bioaccumulation. J. Chem 2019, 6730305 (2019).
Katheresan, V., Kansedo, J., & Lau, S. Y. Efficiency of various recent wastewater dye removal methods: A review. J. Environ. Chem. Eng 6 4676-4697 (2018).
Shabir, M., Yasin, M., Hussain, M., Shafiq, I., Akhter, P., Nizami, A. S., ... & Park, Y. K. A review on recent advances in the treatment of dye-polluted wastewater. J. Ind. Eng. Chem 112, 1-19 (2022).
Jun, L. Y., Yon, L. S., Mubarak, N. M., Bing, C. H., Pan, S., Danquah, M. K., ... & Khalid, M. An overview of immobilized enzyme technologies for dye and phenolic removal from wastewater. J. Environ. Chem. Eng 7, 102961.
Rad, L. R., & Anbia, M. Zeolite-based composites for the adsorption of toxic matters from water: A review. J. Environ. Chem. Eng 9, 106088 (2021).
Abd, A. A., Othman, M. R., & Kim, J. A review on application of activated carbons for carbon dioxide capture: present performance, preparation, and surface modification for further improvement. Environ. Sci. Pollut. Res. Int 28, 43329-43364 (2021).
Zwain, H. M., Vakili, M., & Dahlan, I. (Waste material adsorbents for zinc removal from wastewater: a comprehensive review. Int. J. Chem. Eng 2014 347912 (2014).
Wang, S., & Peng, Y. Natural zeolites as effective adsorbents in water and wastewater treatment. Chemical engineering journal 156, 11-24 (2010).
Shi, L., Du, J., Chen, Z., Megharaj, M., & Naidu, R. Functional kaolinite supported Fe/Ni nanoparticles for simultaneous catalytic remediation of mixed contaminants (lead and nitrate) from wastewater. J. Colloid Interface Sci 428, 302-307.
Wang, S. G., Gong, W. X., Liu, X. W., Yao, Y. W., Gao, B. Y., & Yue, Q. Y. Removal of lead (II) from aqueous solution by adsorption onto manganese oxide-coated carbon nanotubes. Sep. Purif. Technol58, 17-23.
Athab, Z. H., Halbus, A. F., Atiyah, A. J., Ali, S. S. M., & Al Talebi, Z. A. High-performance photocatalytic degradation and antifungal activity of chromium-doped nickel oxide nanoparticles. Anal. Sci 40, 655-670 (2024).
Cai, Z., Dwivedi, A. D., Lee, W. N., Zhao, X., Liu, W., Sillanpää, M., ... & Fu, J. Application of nanotechnologies for removing pharmaceutically active compounds from water: development and future trends. nviron. Sci. Nano 5, 27-47 (2018).
Wan, X., Huang, Y., & Chen, Y. Focusing on energy and optoelectronic applications: a journey for graphene and graphene oxide at large scale. Acc. Chem. Res 45, 598-607 (2012).
Nasir, S., Hussein, M. Z., Zainal, Z., & Yusof, N. A. Carbon-based nanomaterials/allotropes: A glimpse of their synthesis, properties and some applications. Mater 11, 295 (2018).
Compton, O. C., & Nguyen, S. T. Graphene oxide, highly reduced graphene oxide, and graphene: versatile building blocks for carbon‐based materials. small 6, 711-723 (2010).
Loh, K. P., Bao, Q., Eda, G., & Chhowalla, M. Graphene oxide as a chemically tunable platform for optical applications. Nat. Chem 2, 1015-1024 (2010).
Chowdhury, S., & Balasubramanian, R. Recent advances in the use of graphene-family nanoadsorbents for removal of toxic pollutants from wastewater. Adv. Colloid Interface Sci 204 35-56 (2014).
Rathi, B. S., & Kumar, P. S. Application of adsorption process for effective removal of emerging contaminants from water and wastewater. Environ. Pollut 280 116995 (2021).
Singh, S., Barick, K. C., & Bahadur, D. Functional oxide nanomaterials and nanocomposites for the removal of heavy metals and dyes. Nanomater. Nanotechnol 3, 20 (2013).
Singh, S., Anil, A. G., Khasnabis, S., Kumar, V., Nath, B., Adiga, V., ... & Ramamurthy, P. C. Sustainable removal of Cr (VI) using graphene oxide-zinc oxide nanohybrid: Adsorption kinetics, isotherms and thermodynamics. J. Singh, Environ. Res 203, 111891 (2022).
Guo, H., & Barnard, A. S. Naturally occurring iron oxide nanoparticles: morphology, surface chemistry and environmental stability. Chem 1, 27-42 (2013).
Xu, P., Zeng, G. M., Huang, D. L., Feng, C. L., Hu, S., Zhao, M. H., ... & Liu, Z. F. Use of iron oxide nanomaterials in wastewater treatment: a review. Sci. Total Environ 424, 1-10 (2012).
Bhateria, R., & Singh, R. A review on nanotechnological application of magnetic iron oxides for heavy metal removal. J. Water Process Eng 31, 100845 (2019).
Leonel, A. G., Mansur, A. A., & Mansur, H. S. Advanced functional nanostructures based on magnetic iron oxide nanomaterials for water remediation: a review. Water Res 190, 116693 (2021).
Hajipour, A. R., & Rafiee, F. Basic ionic liquids. A short review. J. Iran. Chem. Soc 6, 647-678 (2009).
Nasirpour, N., Mohammadpourfard, M., & Heris, S. Z. Ionic liquids: Promising compounds for sustainable chemical processes and applications. Chem. Eng. Res. Des, 160, 264-300 (2020).
Ramenskaya, L. M., & Grishina, E. P. Intensification phenomenon of weak ionic interactions of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid macro-dispersed in poly (methyl methacrylate): FTIR spectroscopic evidence. J. Phys. Chem. B 112, 4735-4740 (2008).
Zhang, Q., Zhang, S., & Deng, Y. Recent advances in ionic liquid catalysis. Green Chem 13, 2619-2637 (2011).
Freire, M. G., Carvalho, P. J., Fernandes, A. M., Marrucho, I. M., Queimada, A. J., & Coutinho, J. A. Surface tensions of imidazolium based ionic liquids: Anion, cation, temperature and water effect. J.A. Coutinho, J. Colloid Interface Sci 314, 621-630 (2007).
Othman, N. H., Alias, N. H., Shahruddin, M. Z., Bakar, N. F. A., Him, N. R. N., & Lau, W. J. Adsorption kinetics of methylene blue dyes onto magnetic graphene oxide. J. Environ. Chem. Eng 6, 2803-2811 (2018).
Dadvar, F., & Elhamifar, D. Magnetic silica/graphene oxide nanocomposite supported ionic liquid–manganese complex as a powerful catalyst for the synthesis of tetrahydrobenzopyrans. Sci. Rep 13, 19354 (2023).
Singh, N., Riyajuddin, S., Ghosh, K., Mehta, S. K., & Dan, A. Chitosan-graphene oxide hydrogels with embedded magnetic iron oxide nanoparticles for dye removal. ACS Appl. Nano Mater 2, 7379-7392 (2019).
Arslan, M., & Günay, K. Application of 4-VP-g-PET fibers and its N-oxide derivative as an adsorbent for removal of cationic dye. Polym. Bull 76, 953-965 (2019).
Vahidhabanu, S., Adeogun, A. I., & Babu, B. R. Biopolymer-grafted, magnetically tuned halloysite nanotubes as efficient and recyclable spongelike adsorbents for anionic azo dye removal. ACS omega 4, 2425-2436 (2019).
Mittal, H., Babu, R., Dabbawala, A. A., Stephen, S., & Alhassan, S. M. Zeolite-Y incorporated karaya gum hydrogel composites for highly effective removal of cationic dyes. Colloids Surf. A: Physicochem. Eng. Asp 586, 124161 (2020).
Umpleby, R. J., Baxter, S. C., Chen, Y., Shah, R. N., & Shimizu, K. D. Characterization of molecularly imprinted polymers with the Langmuir− Freundlich isotherm. Anal. Chem , 4584-4591 (2001).
Jeppu, G. P., & Clement, T. P. A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects. J. Contam. Hydrol 129, 46-53 (2012).
Norouzi, M., & Elhamifar, D. Magnetic yolk-shell structured methylene and propylamine based mesoporous organosilica nanocomposite: A highly recoverable and durable nanocatalyst with improved efficiency. Colloids Surf. A: Physicochem. Eng. Asp 615, 126226 (2021).
Chung, H. K., Kim, W. H., Park, J., Cho, J., Jeong, T. Y., & Park, P. K. Application of Langmuir and Freundlich isotherms to predict adsorbate removal efficiency or required amount of adsorbent. J. Ind. Eng. Chem 28 , 241-246 (2015).
Dada, A. O., Olalekan, A. P., Olatunya, A. M., Dada, O. J. I. J. C., & Langmuir, F. Temkin and Dubinin–Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk J. Appl. Chem 3 , 38-45 (2012).
Desta, M. B. Batch sorption experiments: Langmuir and Freundlich isotherm studies for the adsorption of textile metal ions onto teff straw (Eragrostis tef) agricultural waste. J. Thermodyn 2013, 375830 (2013).

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You are reading this latest preprint version

Ionic liquid-modified magnetic graphene oxide nanocomposite as a powerful adsorbent for the removal of lead ions and brilliant blue dye

Status:

Version 1

Abstract

Figures

1. Introduction

2. Experimental

2.1. Production of GO@Fe₃O₄@SiO₂-NH₂

2.2. Production of GO@Fe₃O₄@SiO₂-NH₂/IL

2.3. Batch adsorption experiments

3. Results and discussion

3.1. Preparation and characterization of the GO@Fe₃O₄@SiO₂-NH₂/IL adsorbent

3.2. Adsorption studies

3.2.1. Effect of pH

3.2.2. Temperature effect

3.2.3. Contact time effect

3.2.4. Adsorbent dose effect

3.2.5. Effect of the initial concentrations of Pb²⁺ ions and BB dye molecules

3.3. Adsorption isotherms

3.4. Possible mechanism of absorption

4. Conclusion

Declarations

Competing interests

Author Contribution

Acknowledgements

Data Availability

References

Additional Declarations

Status:

Version 1

Ionic liquid-modified magnetic graphene oxide nanocomposite as a powerful adsorbent for the removal of lead ions and brilliant blue dye

Status:

Version 1

Abstract

Figures

1. Introduction

2. Experimental

2.1. Production of GO@Fe3O4@SiO2-NH2

2.2. Production of GO@Fe3O4@SiO2-NH2/IL

2.3. Batch adsorption experiments

3. Results and discussion

3.1. Preparation and characterization of the GO@Fe3O4@SiO2-NH2/IL adsorbent

3.2. Adsorption studies

3.2.1. Effect of pH

3.2.2. Temperature effect

3.2.3. Contact time effect

3.2.4. Adsorbent dose effect

3.2.5. Effect of the initial concentrations of Pb2+ ions and BB dye molecules

3.3. Adsorption isotherms

3.4. Possible mechanism of absorption

4. Conclusion

Declarations

Competing interests

Author Contribution

Acknowledgements

Data Availability

References

Additional Declarations

Status:

Version 1

2.1. Production of GO@Fe₃O₄@SiO₂-NH₂

2.2. Production of GO@Fe₃O₄@SiO₂-NH₂/IL

3.1. Preparation and characterization of the GO@Fe₃O₄@SiO₂-NH₂/IL adsorbent

3.2.5. Effect of the initial concentrations of Pb²⁺ ions and BB dye molecules