بررسی رفتار جذب سرب در حضور کربن‌دات: سینتیک، هم‌دما و ترمودینامیک

نوع مقاله : مقالات پژوهشی

نویسندگان

• جلال صادقی ¹
• امیر لکزیان ¹
• اکرم حلاج نیا ¹
• مینا علیخانی مقدم ²

¹ گروه علوم خاک، دانشکده کشاورزی، دانشگاه فردوسی مشهد، مشهد، ایران

² فارغ‌التحصیل دکتری شیمی، دانشگاه پیام نور

https://doi.org/10.22067/jsw.2024.85220.1357

چکیده

استفاده از جاذب‌های مختلف به‌منظور حذف فلزات سنگین از محیط‌های آبی موضوعی است که به فراوانی در مطالعات مختلف به آن پرداخته شده است. با این وجود همچنان استفاده از جاذب‌های ارزان‌ با قابلیت جذب بالا؛ از جمله موضوعاتی است که در بحث حذف فلزات سنگین از محیط‌های آبی مطرح می‌باشد. در این مطالعه به بررسی تأثیر کربن‌دات قارچی بر سینتیک، هم‌دما و ترمودینامیک جذب سرب پرداخته شد. بدین‌صورت که پس از کشت قارچ Alternaria alternata، اگزوپلی ساکارید این قارچ استخراج و با استفاده از روش هیدروترمال و به کمک اتوکلاو با پوشش تفلون در دمای 200 درجه سلسیوس به‌مدت 24 ساعت به کربن‌دات تبدیل شد. در ادامه جذب سینتیک، هم‌دما و ترمودینامیک جذب سرب توسط این نانو جاذب بررسی شد. در این آزمایش 7 سطح غلظت سرب (100، 200، 300، 400، 500، 750 و 1000 میلی‌گرم در لیتر)، 7 زمان تماس (5، 10، 15، 20، 25، 30 و 60 دقیقه)، 8 سطح pH (2، 4، 6، 7، 8، 9، 10 و 11)، 8 غلظت نانوجاذب (50، 100، 200، 300، 400، 500، 750 و 1000 میلی‌گرم در لیتر)، 3 قدرت یونی محلول (1/0، 01/0 و 001/0 مولار کلرید پتاسیم) و 5 نوع دمای محلول (25، 30، 35، 40 و 45 درجه سلسیوس) بررسی شد. نتایج نشان داد که حداکثر میزان جذب سرب توسط این جاذب 59/13 میلی‌گرم بر گرم بود. از میان مدل­های سینتیک جذب انتخاب شده (شبه مرتبه اول، شبه مرتبه دوم و پخشیدگی درون ذره‌ای)، داده­ها به خوبی توسط مدل شبه مرتبه دوم با 99/0 =R² و 064/0 = RMSE توصیف شد. معادله لنگمویر بهترین برازش را برای هم‌دما جذب سرب در این مطالعه نشان داد که بیانگر جذب تک لایه‌ای و همگن سرب توسط جاذب مورد مطالعه بود. مقادیر مثبت DH° (kJ mol^-1 3/13) و DS (J mol °K^-1 34/70) نشان‌دهنده گرماگیر بودن واکنش و افزایش بی‌نظمی در سطح مشترک جامد-مایع در طول جذب سرب توسط کربن‌دات قارچی بود. مقادیر منفی DG نیز نشان­دهنده خود به خودی بودن واکنش جذب بود.

کلیدواژه‌ها

• اگزوپلی‌ساکارید
• جذب
• فلز سنگین
• نانو جاذب

موضوعات

• علوم خاک

عنوان مقاله [English]

Investigating Lead Adsorption Behavior in the Presence of Carbon Dot (Kinetic, Isotherm and Thermodynamics)

نویسندگان [English]

• J. Sadeghi ¹
• A. Lakzian ¹
• A. Halajnia ¹
• M. Alikhani Moghaddam ²

¹ Department of Soil Science, Faculty of Agriculture, Ferdowsi University of Mashhad, Mashhad, Iran, respectively.

² Graduated with a Ph.D. in Chemistry, Payam Noor University

چکیده [English]

Introduction
The rapid growth of technology, industry, and development of cities has led to an increase in heavy metal pollution in freshwater sources and greywater across the world. The use of different adsorbents in order to remove some heavy metals from aquatic environments is a topic that has been addressed many times in different studies. However, the use of inexpensive absorbents with high adsorption capacity and high efficiency is the priority of many researchers especially when they are discussing the removal of heavy metals from the aquatic environment. Nanomaterials by having exceptional properties such as high efficiency of adsorption, high specific surface area, and fast adsorption can be used to remove metal pollutants from aquatic environments. Carbon dot (CD), among various nanomaterials (carbon-based nanomaterials (CNM), including carbon nanotubes (CNTs), graphene) are suitable adsorbents for heavy metals removal due to their specific surface area and many binding sites. Carbon dots are nanoparticles that lack a specific dimension and fall under the category of carbon nanomaterials, measuring over 10 nm in size. They possess various qualities, including being environmentally friendly, simple to create, highly compatible with living organisms, stable, and capable of switching emission on and off based on the excitation wavelength. Additionally, they can be customized for specific uses due to their high carbon content, which can reach up to 99.9%. These characteristics have generated significant interest among researchers in various fields. In this study, the influence of the fungal carbon dots on the adsorption capacity and kinetics, isotherms, and thermodynamics of lead was investigated.
 
Materials and Methods
Alternaria alternata provided by the Department of Plant Protection at Ferdowsi university of Mashhad. It was recultured and fungal exopolysaccharide was extracted and then was converted into carbon dot using the hydrothermal method. Fungal exopolysaccharide autoclaved in a Teflon container at a temperature of 200 °C. Lead adsorption of synthesized fungal carbon dots was investigated. Lead adsorption tests by fungal carbon dots were performed in laboratory conditions. Lead concentrations (100, 200, 300, 400, 500, 750 and 1000 mg L^-1), contact time (5, 10, 15, 20, 25, 30 and 60 minutes), pH (2, 4, 6, 7, 8, 9, 10 and 11), amount of carbon dots (nanosorbent) (50, 100, 200, 300, 400, 500, 750 and 1000 mg), ionic strength of the solution (0.1, 0.01 and 0.001 M potassium chloride) and solution temperature (25, 30, 35, 40 and 45 °C) was considered for kinetic tests. The data obtained from the kinetic tests were fitted using non-linear regression analysis using Statistica 7.0 software with the kinetic models of intraparticle diffusion, Lagergren (pseudo-first order) and pseudo-second-order. Thermodynamic results were calculated from the data of lead adsorption isotherms at temperatures of 25, 35 and 45 °C. Thermodynamic parameters to analyze the effect of temperature on metal adsorption, such as free energy change, enthalpy change and entropy change, were estimated using thermodynamic equations.
 
Results and Discussion
The initial lead concentration had a great effect on the adsorption rate it by carbon dot, and the highest and lowest percentage of lead adsorption with values of 90.65 and 44.2% were observed in two concentrations of 300 and 1000 mg L^-1 of lead, respectively. With the increase of pH up to 8, the amount of lead adsorption by fungal carbon dot increased significantly. However, with further increase in pH, this trend was reversed and the amount of adsorption decreased. The results showed that lead adsorption by carbon dot increased with the decrease of potassium chloride molarity. By increasing the amount of carbon dot in the solution, the amount of lead adsorption increased, and the highest adsorption was observed at the concentration of 300 mg L^-1 of carbon dot. The results of the experiment also showed that with increase in temperature, the adsorption rate increased at first and then decreased. Based on these results, as the contact time between the absorbent and lead increased, the amount of adsorption by the carbon dots also increased. The maximum adsorption was observed at 25 minutes, which was considered the equilibrium time. As shown in the results, the pseudo-second-order model shows the kinetics of Pb adsorption better than the two pseudo-first-order models and intraparticle diffusion. In this model, R² values are between 0.9989 and 0.9994, and Qe is almost equal to the equilibrium value. According to these results, the decrease of values DG° with the increase in temperature means that the adsorption of lead increases with the increase in temperature, which shows that the adsorption process is more favorable with the increase in temperature, or in other words, it is a spontaneous reaction. Also, the positivity of the reaction enthalpy value (DH°) shows the endothermic nature of the adsorption process. The positivity of the entropy value (DS°) indicates the increase of disorder of the system between the adsorbent material and the solution during the process of lead adsorption by the carbon dot.
 
Conclusion
In total, the results showed that the carbon dot is a very good absorbent for removing lead from the water environment. In the experimental condition when the initial concentration of lead was 300 mg L^-1, temperature was 25 °C, adsorbent concentration was 0.3 g L^-1, reaction time was 25 minutes, and pH 8, the amount of lead adsorption increased significantly. It seems that fungal carbon dot is a safe and relatively cheap adsorbent and suitable for removing lead metal from the solution environment.

کلیدواژه‌ها [English]

• Exopolysaccharide
• Heavy metal
• Nano-absorbent
• Surface adsorption

©2024 The author(s). This is an open access article distributed under Creative Commons Attribution 4.0 International License (CC BY 4.0).

مراجع

1. Abd Rani, U., Ng, L.Y., Ng, C.Y., & Mahmoudi, E. (2020). A review of carbon quantum dots and their applications in wastewater treatment. Advances in Colloid and Interface Science, 278, 102124.
2. Acemioğlu, B. (2004). Removal of Fe (II) ions from aqueous solution by Calabrian pine bark wastes. Bioresource Technology, 93(1), 99–102.
3. Ahmed, I.M., Helal, A.A., El Aziz, N.A., Gamal, R., Shaker, N.O., & Helal, A.A. (2019). Influence of some organic ligands on the adsorption of lead by agricultural soil. Arabian Journal of Chemistry, 12(8), 2540–2547.
4. Alizadeh, B., Ghorbani, M., & Salehi, M.A. (2016). Application of polyrhodanine modified multi-walled carbon nanotubes for high efficiency removal of Pb (II) from aqueous solution. Journal of Molecular Liquids, 220, 142–149.
5. Atchudan, R., Edison, T.N.J.I., Mani, S., Perumal, S., Vinodh, R., Thirunavukkarasu, S., & Lee, Y.R. (2020). Facile synthesis of a novel nitrogen-doped carbon dot adorned zinc oxide composite for photodegradation of methylene blue. Dalton Transactions, 49(48), 17725–17736.
6. Bassyouni, M., Mansi, A.E., Elgabry, A., Ibrahim, B.A., Kassem, O.A., & Alhebeshy, R. (2020). Utilization of carbon nanotubes in removal of heavy metals from wastewater: A review of the CNTs’ potential and current challenges. Applied Physics A, 126, 1–33.
7. Battas, A., El Gaidoumi, A., Ksakas, A., & Kherbeche, A. (2019). Adsorption study for the removal of nitrate from water using local clay. Scientific World Journal. https://doi.org/10.1155/2019/9529618
8. Bhattacharyya, K.G., & Gupta, S.S. (2006). Pb (II) uptake by kaolinite and montmorillonite in aqueous medium: influence of acid activation of the clays. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 277(1–3), 191–200.
9. Burakov, A.E., Galunin, E.V, Burakova, I.V, Kucherova, A.E., Agarwal, S., Tkachev, A.G., & Gupta, V.K. (2018). Adsorption of heavy metals on conventional and nanostructured materials for wastewater treatment purposes: A review. Ecotoxicology and Environmental Safety, 148, 702–712.
10. Cao, Y., & Li, X. (2014). Adsorption of graphene for the removal of inorganic pollutants in water purification: A review. Adsorption, 20(5–6), 713–727. https://doi.org/10.1007/S10450-014-9615-Y
11. Chandraiah, M.R. (2016). Facile synthesis of zero valent iron magnetic biochar composites for Pb (II) removal from the aqueous medium. Alexandria Engineering Journal, 55(1), 619–62
12. Dehghani, M.H., Yetilmezsoy, K., Salari, M., Heidarinejad, Z., Yousefi, M., & Sillanpää, M. (2020). Adsorptive removal of cobalt (II) from aqueous solutions using multi-walled carbon nanotubes and γ-alumina as novel adsorbents: Modelling and optimization based on response surface methodology and artificial neural network. Journal of Molecular Liquids, 299, 112154.
13. Din, S.U., Awan, J.M., Imran, M., Haq, S., Hafeez, M., Hussain, S., & Khan, M.S. (2021). Novel nanocomposite of biochar‐zerovalent copper for lead adsorption. Microscopy Research and Technique, 84(11), 2598-2606.
14. Duan, C., Ma, T., Wang, J., & Zhou, Y. (2020). Removal of heavy metals from aqueous solution using carbon-based adsorbents: A review. Journal of Water Process Engineering, 37, 101339.
15. Dubois, M., Gilles, K.A., Hamilton, J.K., Rebers, P.A., & Smith, F. (1956). Colorimetric method for determination of sugars and related substances. Analytical Chemistry, 28(3), 350–356. https://doi.org/10.1021/ac60111a017
16. Foroughi-Dahr, M., Abolghasemi, H., Esmaili, M., Shojamoradi, A., & Fatoorehchi, H. (2015). Adsorption characteristics of Congo red from aqueous solution onto tea waste. Chemical Engineering Communications, 202(2), 181–193.
17. Freundlich, H. (1906). Adsorption in solution, Phys. Chemical Society, 40, 1361–1368.
18. Giraldo, L., & Moreno-Piraján, J.C. (2008). Pb²⁺ adsorption from aqueous solutions on activated carbons obtained from lignocellulosic residues. Brazilian Journal of Chemical Engineering, 25, 143–151.
19. Guo, T., Bulin, C., Li, B., Zhao, Z., Yu, H., Sun, H., Ge, X., Xing, R., & Zhang, B. (2018). Efficient removal of aqueous Pb (II) using partially reduced graphene oxide-Fe3O4. Adsorption Science & Technology, 36(3–4), 1031–1048.
20. Hadi, P., To, M.-H., Hui, C.-W., Lin, C. S. K., & McKay, G. (2015). Aqueous mercury adsorption by activated carbons. Water Research, 73, 37–55.
21. Hayati, B., Maleki, A., Najafi, F., Daraei, H., Gharibi, F., & McKay, G. (2016). Synthesis and characterization of PAMAM/CNT nanocomposite as a super-capacity adsorbent for heavy metal (Ni2+, Zn2+, As3+, Co2+) removal from wastewater. Journal of Molecular Liquids, 224, 1032–1040.
22. He, Q., Ren, J., & Liu, Y. (2022). Dispersion-assisted tunable fluorescence from carbon dots. Nanotechnology, 33(17), 175705.
23. Helal, A.-A.A. (2006). Removal of mercury from water using pottery. Radiochimica Acta, 94(1), 53–57.
24. Ho, Y.S., McKay, G., Wase, D.A.J., & Forster, C.F. (2000). Study of the sorption of divalent metal ions on to peat. Adsorption Science and Technology, 18(7), 639–650. https://doi.org/10.1260/0263617001493693
25. Huang, Q., Liu, M., Chen, J., Wan, Q., Tian, J., Huang, L., Jiang, R., Wen, Y., Zhang, X., & Wei, Y. (2017). Facile preparation of MoS₂ based polymer composites via mussel inspired chemistry and their high efficiency for removal of organic dyes. Applied Surface Science, 419, 35–44.
26. Kireeti, K.V.M.K., Chandrakanth, G., Kadam, M.M., & Jha, N. (2016). A sodium modified reduced graphene oxide–Fe₃O₄ nanocomposite for efficient lead (II) adsorption. RSC Advances, 6(88), 84825–84836.
27. Lagergren, S. (1898). Zur theorie der sogenannten adsorption geloster stoffe. Kungliga Svenska Vetenskapsakademiens. Handlingar, 24, 1–39.
28. Langmuir, I. (1916). The constitution and fundamental properties of solids and liquids. Part I. Solids. Journal of the American Chemical Society, 38(11), 2221–2295.
29. Li, Z., Chen, J., & Ge, Y. (2017). Removal of lead ion and oil droplet from aqueous solution by lignin-grafted carbon nanotubes. Chemical Engineering Journal, 308, 809–817.
30. Lin, F., Li, C., & Chen, Z. (2018). Exopolysaccharide-derived carbon dots for microbial viability assessment. Frontiers in Microbiology, 9(NOV), 1–10. https://doi.org/10.3389/fmicb.2018.02697
31. Liu, Y., Xiao, N., Gong, N., Wang, H., Shi, X., Gu, W., & Ye, L. (2014). One-step microwave-assisted polyol synthesis of green luminescent carbon dots as optical nanoprobes. Carbon, 68, 258–264.
32. Mahajan, G., & Sud, D. (2014). Nano sized carbonized waste biomass for heavy metal ion remediation. Polish Journal of Chemical Technology, 16(4), 6–13.
33. Mane, V.S., & Babu, P.V.V. (2013). Kinetic and equilibrium studies on the removal of Congo red from aqueous solution using Eucalyptus wood (Eucalyptus globulus) saw dust. Journal of the Taiwan Institute of Chemical Engineers, 44(1), 81–88.
34. Mateos, H., Picca, R.A., Mallardi, A., Dell’Aglio, M., Giacomo, A., De, Cioffi, N., & Palazzo, G. (2020). Effect of the surface chemical composition and of added metal cation concentration on the stability of metal nanoparticles synthesized by pulsed laser ablation in water. Applied Sciences (Switzerland), 10(12), 1–12. https://doi.org/10.3390/ APP10124169
35. Mobasherpour, I., Salahi, E., & Ebrahimi, M. (2012). Removal of divalent nickel cations from aqueous solution by multi-walled carbon nano tubes: equilibrium and kinetic processes. Research on Chemical Intermediates, 38, 2205–2222.
36. Neupane, S., Ramesh, S. T., Gandhimathi, R., & Nidheesh, P.V. (2015). Pineapple leaf (Ananas comosus) powder as a biosorbent for the removal of crystal violet from aqueous solution. Desalination and Water Treatment, 54(7), 2041–2054.
37. Oncsik, T., Trefalt, G., Borkovec, M., & Szilagyi, I. (2015). Specific ion effects on particle aggregation induced by monovalent salts within the Hofmeister series. Langmuir, 31(13), 3799–3807. https://doi.org/10.1021/ACS. 5B00225/SUPPL_FILE/LA5B00225_SI_001.PDF
38. Özsin, G., Kılıç, M., Apaydın-Varol, E., & Pütün, A.E. (2019). Chemically activated carbon production from agricultural waste of chickpea and its application for heavy metal adsorption: equilibrium, kinetic, and thermodynamic studies. Applied Water Science, 9, 1–14.
39. Pacheco, S., Tapia, J., Medina, M., & Rodriguez, R. (2006). Cadmium ions adsorption in simulated wastewater using structured alumina–silica nanoparticles. Journal of Non-Crystalline Solids, 352(52–54), 5475–5481.
40. Pal, A., Bhakat, A., & Chattopadhyay, A. (2019). Zinc ion-induced assembly of crystalline carbon dots with excellent supercapacitor performance. The Journal of Physical Chemistry C, 123(32), 19421–19428.
41. Rahmanian, O., Dinari, M., & Abdolmaleki, M.K. (2018). Carbon quantum dots/layered double hydroxide hybrid for fast and efficient decontamination of Cd (II): The adsorption kinetics and isotherms. Applied Surface Science, 428, 272–279.
42. Ren, X., Zhang, F., Guo, B., Gao, N., & Zhang, X. (2019). Synthesis of N-doped micropore carbon quantum dots with high quantum yield and dual-wavelength photoluminescence emission from biomass for cellular imaging. Nanomaterials, 9(4), 495.
43. Sabet, M., & Mahdavi, K. (2019). Green synthesis of high photoluminescence nitrogen-doped carbon quantum dots from grass via a simple hydrothermal method for removing organic and inorganic water pollutions. Applied Surface Science, 463, 283–291.
44. Sadegh, H., SHahryari, G.R., Masjedi, A., Mahmoodi, Z., & Kazemi, M. (2016). A review on Carbon nanotubes adsorbents for the removal of pollutants from aqueous solutions.
45. Saleh, T.A. (2016). Nanocomposite of carbon nanotubes/silica nanoparticles and their use for adsorption of Pb (II): from surface properties to sorption mechanism. Desalination and Water Treatment, 57(23), 10730–10744.
46. Senthilkumar, R., & Prasad, D.M.R. (2020). Sorption of heavy metals onto biochar. Applications of Biochar for Environmental Safety, 207.
47. Sharma, R., Sarswat, A., Pittman, C.U., & Mohan, D. (2017). Cadmium and lead remediation using magnetic and non-magnetic sustainable biosorbents derived from Bauhinia purpurea RSC Advances, 7(14), 8606–8624.
48. Song, Z., Chen, X., Gong, X., Gao, X., Dai, Q., Nguyen, T.T., & Guo, M. (2020). Luminescent carbon quantum dots/nanofibrillated cellulose composite aerogel for monitoring adsorption of heavy metal ions in water. Optical Materials, 100, 109642.
49. Temnuch, N., Suwattanamala, A., Inpaeng, S., & Tedsree, K. (2021). Magnetite nanoparticles decorated on multi-walled carbon nanotubes for removal of Cu₂⁺ from aqueous solution. Environmental Technology, 42(23), 3572–3580.
50. Vesali-Naseh, M., Khodadadi, A.A., Mortazavi, Y., Moosavi-Movahedi, A.A., & Ostrikov, K. (2016). H₂O/air plasma-functionalized carbon nanotubes decorated with MnO₂ for glucose sensing. RSC Advances, 6(38), 31807–31815.
51. Wang, C., Wang, X., Li, N., Tao, J., Yan, B., Cui, X., & Chen, G. (2022). Adsorption of lead from aqueous solution by biochar: A review. Clean Technologies, 4(3), 629–652.
52. Wang, H., Zhao, X., Han, X., Tang, Z., Liu, S., Guo, W., Deng, C., Guo, Q., Wang, H., Wu, F., Meng, X., & Giesy, J. P. (2017). Effects of monovalent and divalent metal cations on the aggregation and suspension of Fe₃O₄ magnetic nanoparticles in aqueous solution. Science of the Total Environment, 586, 817–826. https://doi.org/10.1016/j. scitotenv.2017.02.060
53. Wanyonyi, W.C., Onyari, J.M., & Shiundu, P.M. (2014). Adsorption of Congo red dye from aqueous solutions using roots of Eichhornia crassipes: kinetic and equilibrium studies. Energy Procedia, 50, 862–869.
54. Yahaya Pudza, M., Zainal Abidin, Z., Abdul Rashid, S., Md Yasin, F., Noor, A.S.M., & Issa, M.A. (2020). Eco-friendly sustainable fluorescent carbon dots for the adsorption of heavy metal ions in aqueous environment. Nanomaterials, 10(2), 315.
55. Yang, B., Yu, C., Yu, Q., Zhang, X., Li, Z., & Lei, L. (2015). N-doped carbon xerogels as adsorbents for the removal of heavy metal ions from aqueous solution. RSC Advances, 5(10), 7182–7191.
56. Yusuf, M., Elfghi, F.M., Zaidi, S.A., Abdullah, E.C., & Khan, M.A. (2015). Applications of graphene and its derivatives as an adsorbent for heavy metal and dye removal: a systematic and comprehensive overview. RSC Advances, 5(62), 50392–50420. https://doi.org/10.1039/C5RA07223A
57. Zhang, X., Huang, Q., Deng, F., Huang, H., Wan, Q., Liu, M., & Wei, Y. (2017). Mussel-inspired fabrication of functional materials and their environmental applications: progress and prospects. Applied Materials Today, 7, 222–238.
58. Zhao, T., Yao, Y., Li, D., Wu, F., Zhang, C., & Gao, B. (2018). Facile low-temperature one-step synthesis of pomelo peel biochar under air atmosphere and its adsorption behaviors for Ag (I) and Pb (II). Science of the Total Environment, 640, 73–79.
59. Zhou, N., Chen, H., Xi, J., Yao, D., Zhou, Z., Tian, Y., & Lu, X. (2017). Biochars with excellent Pb (II) adsorption property produced from fresh and dehydrated banana peels via hydrothermal carbonization. Bioresource Technology, 232, 204–210.