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Synthesis of hierarchical hollow MIL-53(Al)-NH2 as an adsorbent for removing fluoride: experimental and theoretical perspective

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Abstract

The MIL-53(Al)-NH2 was designed to remove fluoride with hierarchical hollow morphology. It was used as an adsorbent for fluoride removal at a wide pH range (1–12) due to the positive zeta potential of MIL-53(Al)-NH2. The pH did not significantly influence the fluoride adsorption into MIL-53(Al)-NH2. However, the adsorbent indicated good adsorption capacity with maximum adsorption of 1070.6 mg g−1. Different adsorption kinetic and thermodynamic models were investigated for MIL-53(Al)-NH2. The adsorption of fluoride into MIL-53(Al)-NH2 followed the pseudo-second-order model and a well-fitted Langmuir model indicating chemical and monolayer adsorption process. When mass transfer model was used at initial concentrations of 100 ppm and 1000 ppm, the rates of conversion were 8.4 × 10−8 and 4.7 × 10−8 m s−1. Moreover, anions such as \( {\mathrm{SO}}_4^{2-} \), \( {\mathrm{PO}}_4^{3-} \), \( {\mathrm{NO}}_3^{-} \), Cl−, and Br− also had less effect on the adsorption of fluoride. Also, experimental and theoretical calculations on adsorption mechanism of MIL-53(Al)-NH2 revealed that the material had good stability and regenerative capacity using alum as regenerant. In a nutshell, the dominant crystal face (1 0 1) and adsorption sites Al, O, and N combined well with F−, HF, and HF2− through density functional theory. It opens a good way of designing hollow MOFs for adsorbing contaminants in wastewater.

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The datasets generated and/or analyzed during the current study are not publicly available due [REASON WHY DATA ARE NOT PUBLIC] but are available from the corresponding author on reasonable request.

References

  • Abánades Lázaro I, Forgan RS (2019) Application of zirconium MOFs in drug delivery and biomedicine. Coord Chem Rev 380:230–259

    Google Scholar 

  • Abazari R, Mahjoub AR, Shariati J (2019) Synthesis of a nanostructured pillar MOF with high adsorption capacity towards antibiotics pollutants from aqueous solution. J Hazard Mater 366:439–451

    CAS  Google Scholar 

  • Abtahi M, Dobaradaran S, Jorfi S, Koolivand A, Khaloo SS, Spitz J, Saeedi H, Golchinpour N, Saeedi R (2019) Age-sex specific disability-adjusted life years (DALYs) attributable to elevated levels of fluoride in drinking water: a national and subnational study in Iran, 2017. Water Res 157:94–105

    CAS  Google Scholar 

  • Cai Q, Turner BD, Sheng D, Sloan S (2018) Application of kinetic models to the design of a calcite permeable reactive barrier (PRB) for fluoride remediation. Water Res 130:300–311

    CAS  Google Scholar 

  • Chen L, Zhang K, He J, Xu W, Huang X, Liu J (2016) Enhanced fluoride removal from water by sulfate-doped hydroxyapatite hierarchical hollow microspheres. Chem Eng J 285:616–624

    CAS  Google Scholar 

  • Chen C, Park S, Su JF, Yu Y, Heo J, Kim K, Huang CP (2019) The adsorption characteristics of fluoride on commercial activated carbon treated with quaternary ammonium salts (Quats). Sci Total Environ 693:133605

    CAS  Google Scholar 

  • Cheng X, Zhang A, Hou K, Liu M, Wang Y, Song C, Zhang G, Guo X (2013) Size- and morphology-controlled NH2-MIL-53(Al) prepared in DMF-water mixed solvents. Dalton Trans 2013(42):13698

    Google Scholar 

  • Cherukumilli K, Maurer T, Hohman JN, Mehta Y, Gadgil AJ (2018) Effective remediation of groundwater fluoride with inexpensively processed Indian bauxite. Environ Sci Technol 52(8):4711–4718

    CAS  Google Scholar 

  • Chigondo M, Kamdem Paumo H, Bhaumik M, Pillay K, Maity A (2018) Hydrous CeO2-Fe3O4 decorated polyaniline fibers nanocomposite for effective defluoridation of drinking water. J Colloid Interface Sci 532:500–516

    CAS  Google Scholar 

  • Choong CE, Wong KT, Jang SB, Nah IW, Choi J, Ibrahim S, Yoon Y, Jang M (2020) Fluoride removal by palm shell waste based powdered activated carbon vs. functionalized carbon with magnesium silicate: Implications for their application in water treatment. Chemosphere 239:124765

    CAS  Google Scholar 

  • Gabbaï GPAF (2019) Phosphonium boranes for the selective transport of fluoride anions across artificial phospholipid membranes. Angew Chem Int Edit 59(13):5298–5302

    Google Scholar 

  • Gan Y, Wang X, Zhang L, Wu B, Zhang G, Zhang S (2019) Coagulation removal of fluoride by zirconium tetrachloride: Performance evaluation and mechanism analysis. Chemosphere. 218:860–868

    CAS  Google Scholar 

  • Gao M, Wang W, Yang H, Ye B (2020) Efficient removal of fluoride from aqueous solutions using 3D flower-like hierarchical zinc-magnesium-aluminum ternary oxide microspheres. Chem Eng J 380:122459

    CAS  Google Scholar 

  • Ghanbari T, Abnisa F, Wan Daud WMA (2020) A review on production of metal organic frameworks (MOF) for CO2 adsorption. Sci Total Environ 707:135090

    CAS  Google Scholar 

  • Hasan Z, Jhung SH (2015) Removal of hazardous organics from water using metal-organic frameworks (MOFs): Plausible mechanisms for selective adsorptions. J Hazard Mater 283:329–339

    CAS  Google Scholar 

  • He J, Cai X, Chen K, Li Y, Zhang K, Jin Z, Meng F, Liu N, Wang X, Kong L, Huang X, Liu J (2016) Performance of a novelly-defined zirconium metal-organic frameworks adsorption membrane in fluoride removal. J Colloid Interface Sci 484:162–172

    CAS  Google Scholar 

  • He J, Cui A, Ni F, Deng S, Shen F, Yang G (2018) A novel 3D yttrium based-graphene oxide-sodium alginate hydrogel for remarkable adsorption of fluoride from water. J Colloid Interface Sci 531:37–46

    CAS  Google Scholar 

  • Huang Z, Zhou A, Wu J, Chen Y, Lan X, Bai H, Li L (2016) Bottom-up preparation of ultrathin 2D aluminum oxide nanosheets by duplicating graphene oxide. Adv Mater 28(8):1703–1708

    CAS  Google Scholar 

  • Kankan M, Uday CG, Palani S (2019) Enhanced capacity of fluoride scavenging from contaminated water by nano-architectural reorientation of cerium-incorporated hydrous iron oxide with graphene oxide. Environ Sci Pollut Res 25:26112–26133

    Google Scholar 

  • Karmakar S, Dechnik J, Janiak C, De S (2016) Aluminium fumarate metal-organic framework: a super adsorbent for fluoride from water. J Hazard Mater 303:10–20

    CAS  Google Scholar 

  • Karmakar S, Bhattacharjee S, De S (2018) Aluminium fumarate metal organic framework incorporated polyacrylonitrile hollow fiber membranes: spinning, characterization and application in fluoride removal from groundwater. Chem Eng J 334:41–53

    CAS  Google Scholar 

  • Ke F, Luo G, Chen P, Jiang J, Yuan Q, Cai H, Peng C, Wan X (2016) Porous metal-organic frameworks adsorbents as a potential platform for defluoridation of water. J Porous Mater 23(4):1065–1073

    CAS  Google Scholar 

  • Kumari U, Behera SK, Siddiqi H, Meikap BC (2020) Facile method to synthesize efficient adsorbent from alumina by nitric acid activation: Batch scale defluoridation, kinetics, isotherm studies and implementation on industrial wastewater treatment. J Hazard Mater 381:120917

    CAS  Google Scholar 

  • Li L, Xu D, Li X, Liu W, Jia Y (2014) Excellent fluoride removal properties of porous hollow MgO microspheres. New J Chem 38(11):5445–5452

    CAS  Google Scholar 

  • Li S, Zhang L, Liang X, Wang T, Chen X, Liu C, Li L, Wang C (2019a) Tailored synthesis of hollow MOF/polydopamine Janus nanoparticles for synergistic multi-drug chemo-photothermal therapy. Chem Eng J 378:122175

    CAS  Google Scholar 

  • Li X, Zhang H, Wang P, Hou J, Lu J, Easton CD, Zhang X, Hill MR, Thornton AW, Liu JZ, Freeman BD, Hill AJ, Jiang L, Wang H (2019b) Fast and selective fluoride ion conduction in sub-1-nanometer metal-organic framework channels. Nat Commun 10(1):2490

    Google Scholar 

  • Li J, Zhang H, Zhang J, Xiao Q, Du X, Qi T (2019c) Efficient removal of fluoride by complexation extraction: mechanism and thermodynamics. Environ Sci Technol 53(15):9102–9108

    CAS  Google Scholar 

  • Li H, Li Y, Li B, Dai Y, Chen X (2020a) Melamine-induced novel MSONs heterostructured framework: controlled-switching between MOF and SOF via a self-assembling approach for rapid uranium sequestration. Chem Eng J 379:122279

    CAS  Google Scholar 

  • Li Y, Wang Y, He L, Meng L, Lu H, Li X (2020b) Preparation of poly(4-vinylpyridine)-functionalized magnetic Al-MOF for the removal of naproxen from aqueous solution. J Hazard Mater 383:121144

    CAS  Google Scholar 

  • Li B, Zheng J, Guo J, Dai C (2020c) A novel route to synthesize MOFs-derived mesoporous dawsonite and application in elimination of Cu(II) from wastewater. Chem Eng J 383:123174

    CAS  Google Scholar 

  • Lin KA, Liu Y, Chen S (2016) Adsorption of fluoride to UiO-66-NH2 in water: stability, kinetic, isotherm and thermodynamic studies. J Colloid Interface Sci 461:79–87

    CAS  Google Scholar 

  • Liu H, Deng S, Li Z, Yu G, Huang J (2010) Preparation of Al–Ce hybrid adsorbent and its application for defluoridation of drinking water. J Hazard Mater 179:424–430

    CAS  Google Scholar 

  • López-Guzmán M, Alarcón-Herrera MT, Irigoyen-Campuzano JR, Torres-Castañón LA, Reynoso-Cuevas L (2019) Simultaneous removal of fluoride and arsenic from well water by electrocoagulation. Sci Total Environ 678:181–187

    Google Scholar 

  • Lu T, Song H, Dong X, Hu J, Lv Y (2017) A highly selective and fast-response photoluminescence humidity sensor based on F− decorated NH2-MIL-53(Al) nanorods. J Mater Chem C 5(36):9465–9471

    CAS  Google Scholar 

  • Lutiane NA, Jorge LM Jr, Valéria VCL, Janaina OG, Sergiane CB, Ednei GP, Thiago ALB, Guilherme LD, Luiz AAP, Tito RSCJ (2020) Removal of fluoride from fertilizer industry effluent using carbon nanotubes stabilized in chitosan sponge. J Hazard Mater 388:122042

    Google Scholar 

  • Ma A, Ke F, Jiang J, Yuan Q, Luo Z, Liu J, Kumar A (2017) Two lanthanide-based metal-organic frameworks for highly efficient adsorption and removal of fluoride ions from water. Cryst Eng Comm 19:2172–2177

    CAS  Google Scholar 

  • Massoudinejad M, Ghaderpoori M, Shahsavani A, Amini MM (2016) Adsorption of fluoride over a metal organic framework UiO-66 functionalized with amine groups and optimization with response surface methodology. J Mol Liq 221:279–286

    CAS  Google Scholar 

  • Mondal P, Purkait MK (2019) Preparation and characterization of novel green synthesized iron-aluminum nanocomposite and studying its efficiency in fluoride removal. Chemosphere. 235:391–402

    CAS  Google Scholar 

  • Ndé-Tchoupé AI, Nanseu-Njiki CP, Hu R, Nassi A, Noubactep C, Licha T (2019) Characterizing the reactivity of metallic iron for water defluoridation in batch studies. Chemosphere. 219:855–863

    Google Scholar 

  • Oveisi M, Asli MA, Mahmoodi NM (2018) MIL-Ti metal-organic frameworks (MOFs) nanomaterials as superior adsorbents: Synthesis and ultrasound-aided dye adsorption from multicomponent wastewater systems. J Hazard Mater 347:123–140

    CAS  Google Scholar 

  • Parwathi P, Yogesh L, Swapnil D, Mohammad K (2019) Synthesis, characterization, and application of iron oxyhydroxide coated with rice husk for fluoride removal from aqueous media. Environ Sci Pollut Res

  • Prabhu SM, Koilraj P, Sasaki K (2017) Synthesis of sucrose-derived porous carbon-doped ZrxLa1-xOOH materials and their superior performance for the simultaneous immobilization of arsenite and fluoride from binary systems. Chem Eng J 325:1–13

    CAS  Google Scholar 

  • Ren C, Yu Z, Phillips BL, Wang H, Ji J, Pan B, Li W (2019) Molecular-scale investigation of fluoride sorption mechanism by nanosized hydroxyapatite using 19F solid-state NMR spectroscopy. J Colloid Interface Sci 557:357–366

    CAS  Google Scholar 

  • Sabrina FL, Andrei VI, Luana P, Guilherme LD, Luiz AAP, Tito RSCJ (2019) Preparation of activated carbon from black wattle bark waste and its application for phenol adsorption. J Environ Chem Eng 9:103396

    Google Scholar 

  • Tolkou AK, Mitrakas M, Katsoyiannis IA, Ernst M, Zouboulis AI (2019) Fluoride removal from water by composite Al/Fe/Si/Mg pre-polymerized coagulants: characterization and application. Chemosphere. 231:528–537

    CAS  Google Scholar 

  • Trana TV, Cao VD, Nguyen VH, Hoang BN, Vo DN, Nguyen TD, Bach LG (2020) MIL-53(Fe) derived magnetic porous carbon as a robust adsorbent for the removal of phenolic compounds under the optimized conditions. J Environ Chem Eng 8:102902

    Google Scholar 

  • Viswanathan N, Sundaram CS, Meenakshi S (2009) Removal of fluoride from aqueous solution using protonated chitosan beads. J Hazard Mater 161(1):423–430

    CAS  Google Scholar 

  • Wang X, Pan S, Zhang M, Qi J, Sun X, Gu C, Wang L, Li J (2019) Modified hydrous zirconium oxide/PAN nanofibers for efficient defluoridation from groundwater. Sci Total Environ 685:401–409

    CAS  Google Scholar 

  • Wei L, Zietzschmann F, Rietveld LC, van Halem D (2020) Fluoride removal by Ca-Al-CO3 layered double hydroxides at environmentally-relevant concentrations. Chemosphere. 243:125307

    CAS  Google Scholar 

  • Xiang H, Ameen A, Shang J, Jiao Y, Gorgojo P, Siperstein FR, Fan X (2020) Synthesis and modification of moisture-stable coordination pillared-layer metal-organic framework (CPL-MOF) CPL-2 for ethylene/ethane separation. Microporous Mesoporous Mater 293:109784

    CAS  Google Scholar 

  • Zari F, Hossein NI, Mahmood T (2019) Removal of fluoride ion from aqueous solutions by titania-grafted β-cyclodextrin nanocomposite. Environ Sci Pollut Res

  • Zhang Y, Jia Y (2016) Preparation of porous alumina hollow spheres as an adsorbent for fluoride removal from water with low aluminum residual. Ceram Int 42(15):17472–17481

    CAS  Google Scholar 

  • Zhang N, Yang X, Yu X, Jia Y, Wang J, Kong L, Jin Z, Sun B, Luo T, Liu J (2014) Al-1,3,5-benzenetricarboxylic metal–organic frameworks: a promising adsorbent for defluoridation of water with pH insensitivity and low aluminum residual. Chem Eng J 252:220–229

    CAS  Google Scholar 

  • Zhang Q, Bolisetty S, Cao Y, Handschin S, Adamcik J, Peng Q, Mezzenga R (2019a) Selective and efficient removal of fluoride from water: in situ engineered amyloid fibril/ZrO2 hybrid membranes. Angew Chem Int Edit 58(18):6012–6016

    CAS  Google Scholar 

  • Zhang Y, Qian Y, Li W, Gao X, Pan B (2019b) Fluoride uptake by three lanthanum based nanomaterials: behavior and mechanism dependent upon lanthanum species. Sci Total Environ 683:609–616

    CAS  Google Scholar 

  • Zhao X, Liu D, Huang H, Zhang W, Yang Q, Zhong C (2014) The stability and defluoridation performance of MOFs in fluoride solutions. Microporous Mesoporous Mater 185:72–78

    CAS  Google Scholar 

  • Zhu X, Yang C, Yan X (2018) Metal-organic framework-801 for efficient removal of fluoride from water. Microporous Mesoporous Mater 259:163–170

    CAS  Google Scholar 

Download references

Funding

This research is financially supported by Key R&D Program of Hunan Province (2018SK2026), the National Key R&D Program of China (2018YFC1802204 and 2016YFC0403003), and National Natural Science Foundation of China (51634010).

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Authors and Affiliations

  1. School of Metallurgy and Environment, Central South University, Changsha, 410083, People’s Republic of China

    Lei Huang, Zhihui Yang, Xiaorui Li, Lanjing Hou, Sikpaam Issaka Alhassan & Haiying Wang

  2. Chinese National Engineering Research Center for Control and Treatment of Heavy Metal Pollution, Changsha, 410083, People’s Republic of China

    Zhihui Yang & Haiying Wang

  3. Water Pollution Control Technology Key Lab of Hunan Province, Changsha, 410004, China

    Haiying Wang

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  1. Lei Huang
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  2. Zhihui Yang
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  3. Xiaorui Li
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  4. Lanjing Hou
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  5. Sikpaam Issaka Alhassan
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Contributions

Lei Huang did the experiment and analyzed and wrote the manuscript. Zhihui Yang revised, and Xiaorui Li and Lanjing Hou helped in the experiment process. Sikpaam Issaka Alhassan checked English in the manuscript. Haiying Wang designed and revised the manuscript. All authors read and approved the final manuscript.

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Correspondence to Haiying Wang.

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Huang, L., Yang, Z., Li, X. et al. Synthesis of hierarchical hollow MIL-53(Al)-NH2 as an adsorbent for removing fluoride: experimental and theoretical perspective. Environ Sci Pollut Res 28, 6886–6897 (2021). https://doi.org/10.1007/s11356-020-10975-x

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