Nashrieh Shimi va Mohandesi Shimi Iran

Nashrieh Shimi va Mohandesi Shimi Iran

Equilibrium isotherms studies of methylene blue adsorption by MIL-101(Cr) modified with zinc oxide nanoparticles

Document Type : Research Article

Authors
Ali Fathi Hasanbarogh 1
Nahid Ghasemi 1
Elham Ezzatzadeh 2
1 Department of Chemistry, Arak Branch, Islamic Azad University, Arak, IRAN
2 Department of Chemistry, Ardabil Branch, Islamic Azad University, Ardabil, IRAN
Abstract
Emerging pollutants from water are a significant concern in modern society, and surface adsorption has been identified as a promising method to eliminate them. Preparation of an effective adsorbent is crucial for the adsorption method. In this study, a new adsorbent of Metal organic frameworks, MIL-101(Cr)@ZnO, was synthesized by modifying MIL 101(Cr) with zinc oxide nanoparticles using the hydrothermal method. The adsorbent was characterized using XRD, FTIR, FESEM, EDX and BET analysis. The adsorbent's efficiency was evaluated by studies of adsorption equilibrium isotherms under optimal conditions pH = 9, amount of adsorbent 0.0035 g, volume 50 ml, time 60 minutes, at different temperatures (60, 40, 35 °C) and concentrations of methylene blue (6, 8, 9, 10, 11 mg/L). The equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin, Alovich, and Dubinin-Radoshkevich(DR) two-parameter equilibrium isotherms models. The obtained results showed that the order of dye adsorption of the studied isotherms is as follows: Dubinin-Radoshkevich>Temkin>Freundlich>Alovich>Langmuir. Additionally, the order showed that the adsorption of methylene blue occurs in a multilayered form. The isotherm of Dubinin-Radoshkevich with the highest correlation coefficient (R2=0.9767) and low average free energy (E=0.975 J/mol) showed that physical adsorption is the dominant process of adsorption. The maximum adsorption capacity of Langmuir isotherm was determined at the temperature of 313 K with the value of qmax=258.7143 mg/g, the separation factor at the same temperature (RL=0.4364) indicating favorable adsorption. The Freundlich adsorption intensity and correlation coefficient values were n=1.3825 and R2=0.879, respectively. The heat of adsorption in the Temkin's model was calculated to be BT=57.192 J/mol, and the highest adsorption capacity was obtained from Elovich's isotherm qmax=333.3333 mg/g. Further, the amount of thermodynamic values showed that the adsorption process of the pollutant is a spontaneous and endothermic process. The present study's evidence indicates that the adsorption of methylene blue follows a physical process.
Keywords
Metal–organic framework
MIL-101(Cr)@ZnO
Adsorption
Methylene blue

Subjects

[1] Heidari, Y., Noroozian, E. Maghsoudi, S., Electrospun Nanofibers of Cellulose Acetate/Metal Organic Framework-Third Generation PAMAM Dendrimer for the Removal of Methylene Blue From Aqueous Media, Sci. Rep., 13: 4924 (2023).
[2] Moosavi S., Lai C.W., Gan S., Zamiri G., Akbarzadeh Pivehzhani O., Johan M.R., Application of Efficient Magnetic Particles and Activated Carbon for Dye Removal from Wastewater, ACS Omega, 5(33): 20684–20697 (2020).
[3] چگنی، مهدیه؛ یوسفوند، حدیث، بررسی تخریب متیلن بلو از محلول­های آبی با استفاده از نانوکامپوزیت پرلیت-کبالت اکسید-گرافن اکسید کاهش یافته، نشریه شیمی و مهندسی شیمی ایران، 40(4): 43 تا 54 (1400).
[4] Kitagawa S., Kitaura R., Noro S., Functional Porous Coordination Polymers, Chem. Int. Ed., 43: 2334-2375 (2004).
[5] Long R., Long O.M., The pervasive Chemistry of Metal–Organic Frameworks, Chem. Soc. Rev., 38: 1213-1214 (2009).
[6] Rosi N.L., Eckert J., Eddaoudi M., Vodak D.T., Kim J., O’Keeffe M., Yaghi O.M., Hydrogen Storage in Microporous Metalorganic Frameworks, Science, 300: 1127-1129 (2003).
[7] Wu H., Zhou W., Yildirim T., High-Capacity Methane Storage in Metal−Organic Frameworks M2(dhtp): The Important Role of Open Metal Sites, J. Am. Chem. Soc., 131: 4995-5000 (2009).
[8] Zacher D., Shekhah O., Woll C., Thin Films of Metal–Organic Frameworks, Chem. Soc. Rev., 38: 1418-1429 (2009).
[9] Yang M., Vajeeston P., Ravindran P., Fjellvag H., Tilset M., Revisiting Isoreticular MOFs of Alkaline Earth Metals: A Comprehensive Study on Phase Stability, Electronic Structure, Chemical Bonding, and Optical Properties of A–IRMOF-1 (A = Be, Mg, Ca, Sr, Ba), Phys. Chem. Chem. Phys., 13:10191-10203 (2011).
[10] Jiang J.M., Xu Q., Porous Metal–Organic Frameworks as Platforms for Functional Applications, Chem. Commun., 47: 3351-3370 (2011).
[11] Sakata Y., Furukawa S., Kondo M.,  Hirai K., Horike N., Takashima Y., Uehara H., Louvain N., Meilikhov M., Tsuruoka T., Tsuruoka, Shape-Memory Nanopores Induced in Coordination Frameworks by Crystal Downsizing, Science, 339: 193-196 (2013).
[12] Furukawa H., Ko N., Go B.Y., Aratani N., Choi S.B., Choi E., Yazaydin A.O., Snurr R.Q., O’Keeffe M.,  Kim J., Ultrahigh Porosity in Metal-Organic Frameworks, Science, 329: 424-428 (2010).
[13] Farha O.K., Yazaydin A.O., Eryazici I., Malliakas C.D., Hauser B.G., Kanatzidis M.G., Nguyen S.T., Snurr R.Q., Hupp J.T., De Novo Synthesis of a Metal-Organic Framework Material Featuring Ultrahigh Surface Area and Gas Storage Capacities, Nat. Chem., 2: 944-948 (2010).
[14] Wang Z., Zhang S., Chen Y., Zhang Z., Ma S., Covalent Organic Frameworks for Separation Applications, Chem. Soc. Rev., 49: 708-735 (2020).
[15] Rogacka J., Seremak A., Luna-Triguero A., Formalik F., Matito-Martos I., Firlej L., Calero S., Kuchta B., High-Throughput Screening of Metal–Organic Frameworks for CO2 and CH4 Separation in the Presence of Water,  Chem. Eng. J., 403: 126392 (2021).
[16] Lin Y., Huang Y., Chen X., Recent Advances in Metal-Organic Frameworks for Biomacromolecule Sensing, Chemosensors, 10: 412 (2022).
[17] Lai C., Wang Z., Qin L., Fu Y., et al., Metal-Organic Frameworks as Burgeoning Materials for the Capture and Sensing of Indoor VOCs and Radon Gases,  Coord. Chem. Rev., 427: 213565 (2021).
[18] Yamada, T., Otsubo, K., Makiura  R., Kitagawa  H, Designer Coordination Polymers: Dimensional Crossover Architectures and Proton Conduction, Chem. Soc. Rev., 42: 6655-6669 (2013).
[19] Sadakiyo  M., Okawa  H., Shigematsu  A., Ohba  M., Yamada  T., Kitagawa  H., Promotion of Low-Humidity Proton Conduction by Controlling Hydrophilicity in Layered Metal-Organic Frameworks,  J. Am. Chem. Soc., 134: 5472-5475 (2012).
[20] Horcajada P., Gref  R., Baati T., Allan P.K., Maurin G., Couvreur  P., Ferey  G., Morris  R.E., Serre C., Metal-Organic Frameworks in Biomedicine, Chem. Rev., 112: 1232-1268 (2012).
[21] Taylor-Pashow  K.M., Della Rocca  J., Xie  Z., Tran  S., Lin W., Postsynthetic Modifications of Iron-Carboxylate Nanoscale Metalorganic Frameworks for Imaging and Drug Delivery,  J. Am. Chem. Soc., 131: 14261-14263 (2009).
[22] Celeste A., Paolone A., Itié J.P.,  Borondics F., Joseph B., Grad O., Blanita G., The Mesoporous Metal–Organic Framework MIL-101 at High Pressure, J. Am. Chem. Soc., 142: 15012-15019 (2020).
[23] Lee Y.R., Kim J., Ahn, W.S., Synthesis of Metal-Organic Frameworks: A Mini Review, Korean J. Chem. Eng., 30: 1667–1680 (2013).
[24] Corma A., García H., Xamena F.X., Engineering Metal Organic Frameworks for Heterogeneous Catalysis, Chem. Rev., 110(8): 4606–4655 (2010).
[25] Kaur H., Devi N., Siwal S.S., Alsanie W.F., Thakur M.K., Thakur V.K., Metal–Organic Framework-Based Materials for Wastewater Treatment: Superior Adsorbent Materials for the Removal of Hazardous Pollutants, ACS Omega, 8(10): 9004–9030 (2023).
[26] Hong D.-Y., Hwang Y.K., Serre C., Férey G., Chang J.-S., Porous Chromium Terephthalate MIL-101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis, Adv. Funct. Mater., 19:1537-1552 (2009).
[27] Zou  M., Dong  M., Zhao  T., Advances in Metal-Organic Frameworks MIL-101(Cr),  Int. J. Mol. Sci., 23:9396 (2022). 
[28] Haghighi E., Zeinali S., Nanoporous MIL-101(Cr) as a Sensing Layer Coated on a Quartz Crystal Microbalance (QCM) Nanosensor to Detect Volatile Organic Compounds (VOCs)†, RSC Adv., 9:24460-24470 (2019).
[29] Arslan I., Balcio glu I. A., Bahnemann D. W., Advanced Chemical Oxidation of Reactive Dyes in Simulated Dyehouse Effluents by Ferrioxalate-Fenton/UV-A and TiO2/UV-A Processes, Dyes Pigments, 47: 207-218 (2000).
[30] Namasivayam C., Maniasamy N., Gayatri  K., Rani M., Ranganathan K., Removal of Dyes from Aqueous Solutions by Cellulosic Waste Orange Peel, Bioresour. Technol., 57: 37-43 (1997).
[31] Kusuma H.S., Aigbe U.O.,  Ukhurebor K.E., Onyancha R.B.,Okundaye B., Simbi I., Ama O.M., Darmokoesoemo H., Widyaningrum B.A., Osibote O.A., Balogun V.A., Biosorption of Methylene Blue Using Clove Leaves Waste Modified with Sodium Hydroxide, Results in Chemistry, 5: 100778 (2023).
[32] Abhinandan S., Dhiraj S., Sonochemically Synthesized Mesoporous Pyrophanite- MnTiO3/TiO2 Nanoparticles: Adsorbent for Removal of Commercial Malachite Green Dye, Iran. J. Chem. Chem. Eng., 41(8):2548-2560 (2022).
[33]  Li  C., Xiong  Z., Zhang  J., Wu  C., The Strengthening Role of the Amino Group in Metal–Organic Framework MIL-53 (Al) for Methylene Blue and Malachite Green Dye Adsorption, Chem. Eng. J., 60:3414-3422 (2015). 
[34] Sadiq  H., Sher  F., Sehar   S., Lima  E.C.,  Zhang   S.,  Iqbal  H.M.N., Zafar  F., Nuhanovićj  M., Green synthesis of ZnO nanoparticles from Syzygium Cumini Leaves Extract with Robust Photocatalysis Applications, J. Mol. Liquids., 335: 116567 (2021).
[35] Narath  S.,  Koroth S.K., Shankar S.S., George  B., Mutta  V.,  Waclawek  S.,  Cernik   M.,  Padil  V.V.T., Varma  R.S., Cinnamomum Tamala Leaf Extract Stabilized Zinc Oxide Nanoparticles, A Promising Photocatalyst for Methylene Blue Degradation, Nanomaterials, 11: 1558 (2021).
[36] Kahsay  M.H., Synthesis and Characterization of ZnO Nanoparticles Using Aqueous Extract of Becium Grandiflorum for Antimicrobial Activity and Adsorption of Methylene Blue, Appl. Water Sci., 11: 1866 (2021).
[37] Muhammad W., Ullah N., Haroon M., Abbasi BH., Optical, Morphological and Biological Analysis of Zinc Oxide Nanoparticles (ZnO NPs) using Papaver Somniferum L, RSC Adv., 9: 29541-29548 (2019).
[38] Jaffri S.B., Ahmad K.S., Neoteric Environmental Detoxification of Organic Pollutants and Pathogenic Microbes Via Green Synthesized ZnO Nanoparticles, Environ. Technol., 40: 3745-3761 (2019).
[39] Motakef Kazemi N., Methylene Blue Adsorption from Aqueous Solution Using Zn2(Bdc)2(Dabco) Metal-Organic Framework and Its Polyurethane Nanocomposite, Iran. J. Chem. Chem. Eng., 41(12): 3950-3962 (2022).
[40] Jawad A.H., Solehah Ahmad Norrahma S., Hamee, B.H., Ismail K., Chitosan-Glyoxal Film as a Superior Adsorbent for Two Structurally Different Reactive and Acid Dyes: Adsorption and Mechanism Study, Int. J. Biol., 135: 569-581 (2019).
[41] Jawad A.H., Sabar S., Azlan Mohd Ishak M., Wilson L.D., Solehah Ahmad Norrahma S., Talari M.K., Farhan A.M., Microwave-Assisted Preparation of Mesoporous Activated Carbon from Coconut (Cocos Nucifera) Leaf by H3PO4-Activation for Methylene Blue Adsorption, Chem. Eng. Commun., 204(10): 1563-5201 (2017).
[42]  Hoon Seo K., Markus J., Soshnikova V., Oh K.H.,  Anandapadmanaban G., Elizabeth Jimenez Perez  Z., Mathiyalagan R., Kim Y.J., Yang D.C., Facile and Green Synthesis of Zinc Oxide Particles by Stevia Rebaudiana and its in Vitro Photocatalytic Activity. Inorg. Nano-Met. Chem., 49: 1-6(2019).
[43] زمان، لادن؛ یوسفی، رامین؛ نیایی فر، محمد؛ حذف رنگ متیلن بلو به کمک نانو ذرات اکسید روی آلاییده شده با سرب، کنفرانس آب، پساب و پسماند، ایران، 6: (1394).
[44] خان محمدی، مرتضی؛ رحمانی، فرهاد؛ رهبر شهروزی، جواد؛ تثبیت نانوذره­ های کاتالیستی نوری TiO2 بر روی جاذب متخلخل مزوروزنه 41-MCM به منظور پاالیش آب آلوده به آنتی بیوتیک تتراسایکلین، نشریه شیمی و مهندسی شیمی ایران، 41(1): 219 تا 233 (1401).
 [45] غیاث آبادی فراهانی، معصومه؛  خانلرخانی، علی؛  کاظم زاد، محمود؛  آقابراری، بهزاد، حذف جذبی BTEX از محلول آبی توسط چارچوب آلی فلزیMOF-199 ، نشریه شیمی و مهندسی شیمی ایران، 40(4): 175 تا 176 (1400).
[46] بابا پور، عزیز، بررسی نانوذره­ های مغناطیسی پوشش داده شده با 15-SBA و گروه ­های عاملی آمین دار به منظور جداسازی فلزهای و + Cr4 و Fe+­3 از محلول­ های آلوده به فلزهای سنگین، نشریه شیمی و مهندسی شیمی ایران،40(3): 37 تا 47 (1400).
[47] اسماعیل زاده، علیرضا ؛ حشمت پور، فلورا؛ عبدی خانی، مرضیه السادات، بررسی کارایی نانو کامپوزیت Sr-Ce-ZnO/Hap در تخریب کاتالیستی نوری آلاینده رودامینB در حضور نور مرئی، نشریه شیمی و مهندسی شیمی ایران، 41(3): 85 تا 96 (1401).
[48] گلبابایی، فریده؛ قهری، اصغر؛ صعودی، محمدرضا؛ رحیمی فروشانی، عباس؛ تیرگر، آرام، مطالعه‌های تعادل و سینتیک جذب زیستی کروم شش ظرفیتی از محلول‌های آبی با استفاده از دانه‌های پلیمر زانتان B82 نشریه شیمی و مهندسی شیمی ایران، 30(2): 11 تا 24 (1390).
[49] Banerjee S., Chattopadyaya M.C., Adsorption Characteristics for the Removal of a Toxic Dye, Tartrazine from Aqueous Solutions by a Low Cost Agricultural by-Product, Arab. J. Chem., 10: 51629-51638 (2017).
[50] Ragadhita R., Nandiyanto A.B.D., How to Calculate Adsorption Isotherms of Particles Using Two-Parameter Monolayer Adsorption Models and Equations, Indones. J. Sci. Technol., 6: 205-234 (2021).
[51] Fu J., Chen Z., Wang M., Zhang J., Han R., Xu Q., Adsorption ( Poly Pamine Micropheres): Kinetics, Isoterm, Thermodynamics and Mechanism Analysis, Chem. Eng. J., 259: 53-61 (2015).
[52] Karimi M.A., Masrouri H., Mirbagheri  M.A., Andishgar  S., Pourshamsi T., Synthesis of a New Magnetic Metal–Organic Framework Nanocomposite and its Application in Methylene Blue Removal from Aqueous Solution, J. Chin. Chem. Soc., 65: 1229-1238 (2018).
[53] Tehrani M.S., Zare-Dorabei R., Competitive Removal of Hazardous Dyes from Aqueous Solution by MIL-68(Al): Derivative Spectrophotometric Method and Response Surface Methodology Approach. Spectrochim. Acta Part A Mol, Biomol. Spectrosc., 160: 8-18 (2016).
[54] Haque E., Jun  J.W., Jhung  S.H., Adsorptive Removal of Methyl Orange and Methylene Blue from Aqueous Solution with a Metal-Organic Framework Material, Iron Terephthalate (MOF-235), J. Hazard. Mater., 185: 507-511 (2011).
[55] Molavi  H., Hakimian  A., Shojaei  A., Raeiszadeh  M., Selective Dye Adsorption by Highly Water Stable Metal-Organic Framework: Long Term Stability Analysis in Aqueous Media, Appl. Surf. Sci., 445: 424-436 (2018).
[56] Beydaghdari  M., Hooriabad Saboor  F., Babapoor  A., Karve, V.V., Asgari  M., Recent Advances in MOF-Based Adsorbents for Dye Removal from the Aquatic Environment, Energies, 15: 2023 (2022).
[57] Eltaweila  A.S., El-Monaema E.M.A., Omer A.M., Khalifaa R. E., El-Latifc M.M.A., El-Subruiti G.M., Efficient Removal of Toxic Methylene Blue (MB) Dye from Aqueous Solution Using a Metal-Organic Framework (MOF) MIL-101(Fe): Isotherms, Kinetics, and Thermodynamic Studies, Desalination Water Treat, 189: 395–407 (2020).
[58]  Xue Y., Xiang P., Wang H., Jiang Y., Long Y., Lian H., Shi W., Mechanistic Insights into Selective Adsorption and Separation of Multi-Component Anionic Dyes Using Magnetic Zeolite Imidazolate Framework-67 Composites, J. Mol. Liq. 296: 111990  (2019).
[59] Zhang  G.,  Wo  R.,  Sun Z.,  Hao  G.,  Liu  G.,  Zhang Y.,  Guo  H.,  Jiang W., Effective Magnetic MOFs Adsorbent for the Removal of Bisphenol A, Tetracycline, Congo Red and Methylene Blue Pollutions, Nanomaterials, 11(8): 1917 (2021).
[60] Elsherbiny A.S., Rady A., Abdelhameed R.M., Gemeay A.H., Efficiency and Selectivity of Cost-Effective Zn-MOF for Dye Removal, Kinetic and Thermodynamic Approach, Environ. Sci. Pollut. Res., (2023). 
[61] Hajnaja M., Khorshidi A., Gilani A.G., Verpoort F., Removal of Methylene Blue from Aqueous Solution by Polydopamine@Zeolitic Imidazolate-67, Res. Sq, (2021).
[62] Soni S., Bajpai P.K., Mittal J., Arora C., Utilisation of Cobalt Doped Iron Based MOF for Enhanced Removal and Recovery of Methylene Blue Dye from Waste Water, J. Mol. Liq., 314: 113642–113654 (2020).
[63] Ahmadijokani F., Molavi H., Bahi A., Wuttke S., Kamkar M., Rojas O.J.,Ko F., Arjmand.M., Electrospun Nanofbers of Chitosan/Polyvinyl Alcohol/UiO-66/ Nanodiamond: Versatile Adsorbents for Wastewater Remediation and Organic Dye Removal, Chem. Eng. J., 457(1): 141176 (2023).
[64]  وثوقی، مهدی؛ عین اله زاده، نگار، بررسی کارایی فرایند جذب Zeolite@ZnO در حذف رنگ متیلن بلو از محلول‌های آبی، طلوع بهداشت، ۲۰(۴): ۷۹ تا 92 (1400).
[65] Zhang H., Shi X., Li J., Kumar P., Liu B., Selective dye Adsorption by Zeolitic Imidazolate Framework-8loadedUiO-66-NH2, Nanomaterials, 9: 1283 (2019).