Defluoridation of Aqueous Solution by Graphene and Graphene Oxide Nanoparticles: Thermodynamic and Isotherm Studies

Document Type: Research Article


1 Department of Engineering, College of Natural Resources, Islamic Azad University, Bandar Abbas Branch, Bandar Abbas, I.R. IRAN

2 Naghizadeh, Ali*+ Medical Toxicology and Drug Abuse Research Center (MTDRC), Birjand University of Medical Sciences (BUMS), Birjand, I.R. IRAN


Fluoride, a non-essential element, can enter water resources through several natural processes and human activities. The benefits and risks of fluoride depend on the concentration of this anion on drinking waters. In the present study, the performances of graphene and graphene oxide nanoparticles were investigated for the removal of fluoride from aqueous solution. In the present research, effects of pH, contact time, fluoride initial concentration, adsorbents dosage, as well as temperature in performance of graphene and graphene oxide nanoparticles in removal of fluoride from aqueous solution were examined. Also, isotherms and thermodynamics of the adsorption process were evaluated. For both adsorbents, the maximum adsorption capacities observed during the first 15 minutes at pH=3 and an initial fluoride concentration of 10 mg/L. The results also showed that adsorption of fluoride by graphene and graphene oxide fitted well with Freundlich and Langmuir isotherms, respectively. Furthermore, temperature increase resulted in the adsorption capacity decrease, indicating an exothermic adsorption reaction. According to the results of this research, graphene nanoparticles have higher adsorption capacity of fluoride than graphene oxide nanoparticles.


Main Subjects

[1] Amini M., Mueller K., Abbaspour K.C., Rosenberg T., Afyuni M., Sarr M., Johnson C.A., Statistical Modeling of Global Geogenic Fluoride Contamination in Groundwaters, Environ Sci Technology, 42: 3662–3668 (2008).
[2] Qasim S., Edward R., Motley M., Guang Z., Water Works Engineering: Planning, Design and Opration, (2005).
[3] Cengeloglu Y., Klr E., Ersoz M., Removal of Fluoride from Aqueous Solution by Using Red Mud, Separation and Purification Technology, 28: 81–86(2002).
[4] Rao C.R., Nagendra, Fluoride and Environment- A Review, Proceedings of the Third International Conference on Environment and Health, Chennai, India, 386 – 399(2003).
[5] Mahramanlioglu M., Kizilcikli I., Bicer I.O., Adsorption of Fluoride from Aqueous Solution by Acid Treated Spent Bleaching Earth, Journal of Fluorine Chemistry, 115: 41-49(2002).
[6] Jamodei A.V., Sapkal V.S., Jamode V.S., Defluoridation of Water Using Inexpensive Adsorbents, Journal  Ind Inst Sci. 84: 163–171 (2004).
[7] Fan X., Parker D.J., Smith M.D., Adsorption Kinetics of Fluoride on Low Cost Materials, Water Res., 37: 4929–4937(2003).
[8] Islam M., Patel R.K., Thermal Activation of Basic Oxygen Furnace Slag and Evaluation of Its Fluoride Removal Efficiency, Chem. Eng. Journal, 169: 68–77(2011).
[9] Letterman D., “Water Quality and Treatment: A Handbook of Community Water Supplies”, McGraw-Hill, New York (1999).
[10] Turner B.D., Binning P., Stipp S., Fluoride Removal by Calcite: Evidence for Fluorite Precipitation and Surface Adsorption, Environ Sci. Technology, 39: 9561–9568 (2005).
[11] Ndiaye P.I., Moulin P., Dominguez L., Millet J.C., Charbit F., Removal of Fluoride from Electronic Industrial Effluent by RO Membrane Separation, Desalination, 173: 25–32(2005).
[12] Tahaikt M., Achary I., Menkouchi Sahli M.A., Amor Z., Taky M., Alami A., Boughriba A., Hafsi M., Elmidaoui A., Defluoridation of Moroccan Groundwater by Electrodialysis: Continuous Operation, Desalination, 189: 215–220(2006).
[13] Kodama H., Kabay N., Reactivity of Inorganic Anion Exchanger BiPbO2(NO3) with Fluoride Ions in Solution, Solid State Ion, 141-142: 603–607 (2001).
[14] Tomar V., Kumar D., A Critical Study on Efficiency of Different Materials for Fluoride Removal from Qqueous Media, Chemistry Central Journal, 7:(2013).
[15] Leyva Ramos R., Ovalle-Turrubiartes J., Sanchez-Castillo M.A., Adsorption of Fluoride from Aqueous Solution on Aluminum-Impregnated Carbon, Elsevier Science Ltd, 37: 609–617(1999).
[16] Bhatnagar A., Kumar E., Sillanpaa M., Fluoride Removal from Water by Adsorption—A Review, Chem. Eng. J., 171: 811–840(2011).
[17] Wu X., Zhang Yu., Dou X., Yang M., Fluoride Removal Performance of a Novel Fe–Al–Ce Trimetal Oxide Adsorbent, Chemosphere, 69(11): 1758-1764 (2007).
[18] Bazrafshan E., Khoshnamvand N., Mahvi A., Fluoride Removal from Aqueous Environments by ZnCl2 Treated Eucalyptus Leaves as a Natural Adsorbent, Fluoride, 48: 315-320 (2015).
[19] Daifullah A., Yakout S., Elreefy S., Adsorption of Fluoride in Aqueous Solutions using KMnO4-Modified Activated Carbon Derived from Steam Pyrolysis of Rice Straw, Hazardous Material, 147: 633-643(2007).
[20] Chen N., Zhang Z., Feng C., Li M., Zhu Z., Chen R., Sugiura N. An Excellent fluoride Sorption Behavior of Ceramic Adsorbent, Journal of Hazardous Materials, 183(1-3): 460-465 (2010).
[21] Sheshmani S.H., Arab Fashapoyeh M., Amini R., Iron (iii) Hydroxide/Graphene Oxide Nano Composite and Investigation of Lead Adsorption, Quarterly Journal of Applied Researches in Chemistry (JARC), 6: 17-23(2013).
[22] Saghapour Y., Aghaie M., Zare K., Thermodynamic Study of Lead Ion Removal by Adsorption on to Nanographene Sheets, Journal of Physical and Theoretical Chemistry of Islamic Azad University of Iran, 10: 59-67(2013).
[24] Chai L., Wang Y., Zhao N., Yang W., You X., Sulfate-Doped Fe3O4/Al2O3 Nanoparticles as a Novel Adsorbent for Fluoride Removal from Drinking Water, Water Research, 47(12): 4040-4049 (2013).
[26] Mahvi A.H., Rahmani Boldaji M., Dobaradaran S., Evaluating the Performance of Tron Nano-Particle Resin in Removing Fluoride from Water, Water and Wasewater J., 21: 33-37 (2010).
[27] Lu J., Li Y., Yan X., Shi B., Wang D., Tang H., Sorption of Atrazine onto Humic Acids (HAs) Coated Nanoparticles, Colloids Surf A Physicochem Eng Asp., 347: 90-96 (2009).
[30] Ghorai S., K.K. P., Equilibrium, Kinetics and Breakthrough Studies for Adsorption of Fluoride on Activated Alumina, Separation and Purification Technology, 42: 265–271 (2005).
[31] Takaaki W., Yuta U., Shuji N., Katsuyasu S., Adsorption Behavior of Fluoride Ions Using a Titanium Hydroxide-Derived Adsorbent, Desalination, 249: 323-330 (2009).
[32] Ramdani A., Taleb S., Benghalem A., Ghaffour N., Removal of Excess Fluoride Ions from  Saharan Brackish Water by Adsorption on Natural Materials, Desalination, 250: 408–413 (2010).
[33] Nan C., Zhenya Z., Chuanping F., Dirui Z., Yingnan Y., Norio S., Preparation and Characterization of Porous Granular Ceramic Containing Dispersed Aluminum and Iron Oxides as Adsorbents for Fluoride Removal from Aqueous Solution, J. Hazard Mater, 186: 863-868 (2011).
 [34] Xiaotian X., Qin L., Hao C., Jianfeng P., Li S., Hao A., Jianping Z., Adsorption of Fluoride from Aqueous Solution on Magnesia-Loaded Fly Ash Cenospheres, Desalination, 272: 233-239 (2011).
[35] Dehghani M.H., Haghighat G.A., Yetilmezsoy K., Mckay G., Heibati B., Tyagi I., Agarwal S., Gupta V., Adsorptive Removal of Fluoride from Aqueous Solution Using Single- and Multi-walled Carbon Nanotubes, Journal of Molecular Liquids, 216: 401-410 (2016)
[36] Venkataraman S., Thiyagarajan R., Andre D., Manganese Dioxide Improves the Efficiency of Earthenware in Fluoride Removal from Drinking Water, Desalination, 272: 179-186 (2011).
[37] Karthikeyan G., Siva Ilango S., Fluoride Sorption Using Morringa indica-Based Activated Carbon, Iran J. Enviton Health Sci Eng., 4: 21-28 (2007).
[38] Pandey P., Pandey M., Sharma R., Defluoridation of Water by a Biomass: Tinospora cordifolia, J. Environ Prot., 3: 610-616(2012).
[39] Salifu A., Petrusevski B., Ghebremichael K., Modestus L., Buamah R., Aubry C., Aluminum (hydr)Oxide Coated Pumice for Fluoride Removal from Drinking Water: Synthesis, Equilibrium, Kinetics and Mechanism, Chem. Eng. J., 228: 63-74 (2013).
[40] Mourabet M., El Rhilassi A., El Boujaady H., Bennani-Ziatni M., El Hamri R., Taitai A., Removal of Fluoride from Aqueous Solution by Adsorption on Apatitic Tricalcium Phosphate Using Box–Behnken Design and Desirability Function., Appl. Surf. Sci., 258: 4402-4410 (2012).
[41] Zhang Z., Tan Y., Zhong M., Defluorination of Wastewater by Calcium Chloride Modified Natural Zeolite, Desalination, 276: 246-252 (2011).
[42] Yu X., Tong S., Ge M., Zuo J., Removal of Fluoride from Drinking Water by cellulose@hydroxyapatite Nanocomposites., Carbohydr Polym., 92: 269-275 (2013).
[43] Babaeivelni K., Khodadoust A., Adsorption of Fluoride onto Crystalline Titanium Dioxide: Effect of pH, Ionic Strength, and co-Existing Ions, J. Colloid Interface Sci., 394: 419-427 (2013).
[44] Ishihara T., Shuto Y., Ueshima S., Ngee H., Nishiguchi H., Takita Y., Titanium Hydroxide as a New Inorganic Fluoride Ion Exchanger., J. Ceram Soc. Jpn., 110: 801-803 (2002).
[45] Chai L., Wang Y., Zhao N., Yang W., You X., Sulfate-Doped Fe3O4/Al2O3 Nanoparticles as a Novel Adsorbent for Fluoride Removal from Drinking Water, Water Res., 47: 4040