Aluminosilicate Inorganic Polymers (Geopolymers): Emerging Ion Exchangers for Removal of Metal Ions

  • Bassam I. El-EswedEmail author


Geopolymers (GPs), also known as alkali-activated aluminosilicates or inorganic polymers, are synthesized from an aluminosilicate source (fly ash, metakaolin, or blast furnace slag) and very alkaline sodium hydroxide and/or silicate. Due to their high compressive strength, acid and fire resistance, GPs are used as construction and coating materials. However, since the structure of GP contains negatively charged Al(III) tetrahedra (balanced by alkali cations), they are feasible ion exchangers. The present chapter is aimed to encapsulate the developments in the field of using GPs for the removal of alkali metals (Li+, K+, Cs+), alkaline earth metals (Mg2+, Ca2+, Sr2+, and Ba2+), ammonium ion, and heavy metals (Pb2+, Cu2+, Cd2+, Zn2+, Ni2+, Cr3+) from water. GPs are the first cementing materials that have remarkable ion exchange capacity. GPs have higher ion exchange/adsorption capacity, but a lower rate of adsorption than their precursors (fly ash, metakaolin,…). Thus, geopolymerization increases the adsorption sites on one hand but imposes kinetics limitations that render GPs slow adsorption. GPs resemble zeolites in respect of cation exchange capacity, high surface area, and thermal stability. However, the synthesis of GPs is easier and inexpensive with lower energy and water demand than zeolite synthesis. The prepared GP could be directly formulated as high compressive strength granules at a low temperature. Since GPs are more acid resistant, they are accessible for regeneration than zeolites, but this issue requires further work.


Aluminosilicate inorganic polymers Geopolymers Inorganic cation exchangers Cesium Ammonium Strontium Heavy metals Adsorption 



Brunauer–Emmett–Teller (BET) theory


Blast furnace slag from iron manufacturing


Cation exchange capacity (meq/mol)


Energy-dispersive X-ray spectroscopy


Fly ash from electricity plant employing coal (low calcium, type F)




Pseudo-second-order rate constant (g mg−1 min−1)


Langmuir affinity constant (L mg−1)




Adsorption capacity (mg g−1)


Scanning electron micrographs


X-ray diffraction


  1. 1.
    Davidovits J (1991) Geopolymers: inorganic polymeric new materials. J Therm Anal 37:1633–1656CrossRefGoogle Scholar
  2. 2.
    Provis JL, Fernández-Jiménez A, Kamseu E, Leonelli C, Palom A (2014) Binder chemistry—low-calcium alkali-activated materials. In: Provis JL, van Devente JSJ (eds) Alkali activated materials: state-of-the-art report, RILEM TC 224-AAM, Springer, pp 93–123Google Scholar
  3. 3.
    Ducman V, Korat L (2016) Characterization of geopolymer fly-ash based foams obtained with the. Mater Charact 113:207–213. Scholar
  4. 4.
    Melar J, Renaudin G, Leroux F, Hardy-Dessources A, Nedelec J, Taviot-Gueho C, Petit E, Steins P, Poulesquen A, Frizon F (2015) The porous network and its interface inside geopolymers as a function of alkali cation and aging. J Phys Chem C 119(31):17619–17632. Scholar
  5. 5.
    Zhang L, Zhang F, Liu M, Hu X (2017) Novel sustainable geopolymer based syntactic foams: an eco-friendly alternative to polymer based syntactic foams. Chem Eng J 313:74–82. Scholar
  6. 6.
    Zhang Z, Provis JL, Reid A, Wang H (2014) Geopolymer foam concrete: an emerging material for sustainable construction. Constr Build Mater 56:113–127. Scholar
  7. 7.
    Zhang F, Zhang L, Liu M, Mu C, Liang YN, Hu X (2017) Role of alkali cation in compressive strength of metakaolin based geopolymers. Ceram Int 43(4):3811–3817. Scholar
  8. 8.
    Duxson P, Fernandez-Jimenez A, Provis JL, Lukey GC, Palomo A, Van Deventer JSJ (2007) Geopolymer technology: the current state of the art. J Mater Sci 42:2917–2933CrossRefGoogle Scholar
  9. 9.
    Vance ER, Perera DS (2009) Geopolymers for nuclear waste immobilization. In: Provis JL, Van Deventer JSJ (eds) Geopolymers: structure, processing, properties and industrial applications. CRC Press and Woodhead Publishing Limited, Oxford, pp 401–420CrossRefGoogle Scholar
  10. 10.
    Wang Y, Han F, Mu J (2018) Solidification/stabilization mechanism of Pb(II), Cd(II), Mn(II) and Cr(III) in fly ash based geopolymers. Constr Build Mater 160:818–827. Scholar
  11. 11.
    Waijarean N, MacKenzie KJD, Asavapisit S, Piyaphanuwat R, Jameson GNL (2017) Synthesis and properties of geopolymers based on water treatment residue and their immobilization of some heavy metals. J. Mater. Sci. 52(12):7345–7359. Scholar
  12. 12.
    El-Eswed BI, Aldagag OM, Khalili FI (2017) Efficiency and mechanism of stabilization/solidification of Pb(II), Cd(II), Cu(II), Th(IV) and U(VI) in metakaolin based geopolymers. Appl Clay Sci 140:148–156. Scholar
  13. 13.
    El-Eswed BI (2018) Solidification versus adsorption for immobilization of pollutants in geopolymeric materials: a review, solidification. Ares A (ed) InTech. Available from: Scholar
  14. 14.
    Al-Mashqbeh A, Abuali S, El-Eswed B, Khalili FI (2018) Immobilization of toxic inorganic anions (Cr2O72-, MnO4- and Fe(CN)63-) in metakaolin based geopolymers: A preliminary study. Ceram Int 44(5):5613–5620. Scholar
  15. 15.
    Davidovits J (2017) Geopolymers: ceramic-like inorganic polymers. J Ceram Sci Technol 08:335–350. Scholar
  16. 16.
    Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156(1):2–10. Scholar
  17. 17.
    Tan KL, Hameed BH (2017) Insight into the adsorption kinetics models for the removal of contaminants from aqueous solutions. J Taiwan Inst Chem Eng 74:25–48. Scholar
  18. 18.
    Bortnovsky O, Dědeček J, Tvarůžková Z, Sobalík Z, Šubrt J (2008) Metal ions as probes for characterization of geopolymer materials. J Am Ceram Soc 91:3052–3057. Scholar
  19. 19.
    Skorina T (2014) Ion exchange in amorphous alkali-activated aluminosilicates: potassium based geopolymers. Appl Clay Sci 87:205–211. Scholar
  20. 20.
    Luukkonen T, Věžníková K, Tolonen E, Runtti H, Yliniemi J, Hu T, Kemppainen K, Lassi U (2017) Removal of ammonium from municipal wastewater with powdered and granulated metakaolin geopolymer. Environ Technol:1–10. Scholar
  21. 21.
    Yuan J, He P, Jia D, You J, Liu X, Zhang Y, Cai D, Yang Z, Duan X, Wang S, Zhou Y (2017) Effects of Na + substitution Cs + on the microstructure and thermal expansion behavior of ceramic derived from geopolymer. J Am Ceram Soc 100:4412–4424. Scholar
  22. 22.
    Arbel Haddad M, Ofer-Rozovsky E, Bar-Nes G, Borojovich EJC, Nikolski A, Mogiliansky D, Katz A (2017) Formation of zeolites in metakaolin-based geopolymers and their potential application for Cs immobilization. J Nucl Mater 493:168–179. Scholar
  23. 23.
    López FJ, Sugita S, Tagaya M, Kobayashi T (2014) Metakaolin-based geopolymers for targeted adsorbents to heavy metal ion separation. J Mater Sci Chem Eng 2:16–27. Scholar
  24. 24.
    Lee NK, Khalid HR, Lee HK (2017) Adsorption characteristics of cesium onto mesoporous geopolymers containing nano-crystalline zeolites. Microporous Mesoporous Mater 242:238–244. Scholar
  25. 25.
    O’Connor SJ, MacKenzie KJD, Smith ME, Hanna JV (2010) Ion exchange in the charge-balancing sites of aluminosilicate inorganic polymers. J Mater Chem 20:10234–10240. Scholar
  26. 26.
    Luukkonen T, Tolonen E, Runtti H, Kemppainen K, Perämäki P, Rämö J, Lassi U (2017) Optimization of the metakaolin geopolymer preparation for maximized ammonium adsorption capacity. J Mater Sci 16. Scholar
  27. 27.
    Belchinskaya L, Novikova L, Khokhlov V, Tkhi JL (2013) Contribution of ion-exchange and non-ion-exchange reactions to sorption of ammonium ions by natural and activated aluminosilicate sorbent. J Appl Chem:1–9. Scholar
  28. 28.
    Uehara M, Isogaya S, Yamazaki A (2008) Ion-exchange properties of hardened geopolymers paste from fly ash. Clay Sci 14(3):127–133.
  29. 29.
    Cheng TW, Lee ML, Ko MS, Ueng TH, Yang SF (2012) The heavy metal adsorption characteristics on metakaolin-based geopolymer. Appl Clay Sci 56:90–96. Scholar
  30. 30.
    Kara İ, Yilmazer D, Akar STI (2017) Metakaolin based geopolymer as an effective adsorbent for adsorption of zinc(II) and nickel(II) ions from aqueous solutions. Appl Clay Sci 139:54–63. Scholar
  31. 31.
    Tang Q, Ge Y, Wang K, He Y, Cui X (2015) Preparation and characterization of porous metakaolin-based inorganic polymer spheres as an adsorbent. Mater Des 88:1244–1249. Scholar
  32. 32.
    Ge Y, Cui X, Kong Y, Li Z, He Y, Zhou Q (2015) Porous geopolymeric spheres for removal of Cu(II) from aqueous solution: synthesis and evaluation. J Hazard Mater 283:244–251. Scholar
  33. 33.
    Luukkonen T, Runtti H, Niskanen M, Tolonen E, Sarkkinen M, Kemppainen K, Ramo J, Lassi U (2016) Simultaneous removal of Ni(II), As(III), and Sb(III) from spiked mine effluent with metakaolin and blast-furnace-slag geopolymers. J Environ Manage 166:579–588. Scholar
  34. 34.
    Medpelli D, Sandoval R, Sherrill L, Hristovski K, Seo D (2015) Iron oxide-modified nanoporous geopolymers for arsenic removal from ground water. Resour-Effi Technol 1(1):19–27. Scholar
  35. 35.
    Wang S, Li L, Zhu ZH (2007) Solid-state conversion of fly ash to effective adsorbents for Cu removal from wastewater. J Hazard Mater 139(2):254–259. Scholar
  36. 36.
    Al-Zboon K, Al-Harahsheh MS, Bani Hani F (2011) Fly ash-based geopolymer for Pb removal from aqueous solution. J Hazard Mater 188:414–421. Scholar
  37. 37.
    Al-Harahsheh MS, Al Zboon K, Al-Makhadmeh L, Hararah M, Mahasneh M (2015) Fly ash based geopolymer for heavy metal removal: A case study on copper removal. J Environ Chem Eng 3(3):1669–1677. Scholar
  38. 38.
    Mužek MN, Svilović S, Zelić J (2013) Fly ash-based geopolymeric adsorbent for copper ion. Desalin Water Treat 52:2519–2526. Scholar
  39. 39.
    Mužek MN, Svilović S, Zelić J (2016) Kinetic studies of cobalt ion removal from aqueous solutions using fly ash-based geopolymer and zeolite NaX as sorbents. Sep Sci Technol 51(18):2868–2875. Scholar
  40. 40.
    Muzek MN, Svilovic S, Ugrina M, Zelic J (2016) Removal of copper and cobalt ions by fly ash-based geopolymer from. Desalin Water Treat 57:10689–10699. Scholar
  41. 41.
    Liu Y, Yan C, Zhang Z, Wang H, Zhou S, Zhou W (2016) A comparative study on fly ash, geopolymer and faujasite block for Pb removal from aqueous solution. Fuel 185:181–189. Scholar
  42. 42.
    Duan P, Yan C, Zhou W, Ren D (2016) Development of fly ash and iron ore tailing based porous geopolymer for removal of Cu(II) from wastewater. Ceram Int 42(12):13507–13518. Scholar
  43. 43.
    Yousef RI, El-Eswed B, Alshaaer M, Khalili F, Khoury H (2009) The influence of using Jordanian natural zeolite on the adsorption, physical, and mechanical properties of geopolymers products. J Hazard Mater 165:379–387. Scholar
  44. 44.
    El-Eswed B, Yousef RI, Alshaaer M, Khalili F, Khoury H (2009) Alkali solid-state conversion of kaolin and zeolite to effective adsorbents for removal of lead from aqueous solution. Desalin Water Treat 8:124–130. Scholar
  45. 45.
    El-Eswed B, Alshaaer M, Yousef RI, Hamadneh I, Khalili F (2012) Adsorption of Cu(II), Ni(II), Zn(II), Cd(II) and Pb(II) onto Kaolin/Zeolite based- geopolymers. Adv Mater Phys Chem 2:119–125. Scholar
  46. 46.
    Alzboon K, Al Smadi B, Al-Khawaldh S (2016) Natural volcanic tuff-based geopolymer for Zn removal: adsorption isotherm, kinetic, and thermodynamic study. Water Air Soil Pollut:227–248.
  47. 47.
    Papa E, Medri V, Amari S, Manaud J, Benito P, Vaccari A, Landi E (2018) Zeolite-geopolymer composite materials: production and characterization. J Clean Prod 171:76–84. Scholar
  48. 48.
    Alshaaer M, Zaharaki D, Komnitsas K (2014) Microstructural characteristics and adsorption potential of a zeolitic tuff–metakaolin geopolymer. Desalin Water Treat 56(2):338–345. Scholar
  49. 49.
    Andrejkovičov S, Sudagar A, Rocha J, Patinha C, Hajjaji W, Ferreira da Silva E, Velosa A, Rocha F (2016) The effect of natural zeolite on microstructure, mechanical and heavy metals adsorption properties of metakaolin based geopolymers. Appl Clay Sci 126:141–152. Scholar
  50. 50.
    Li L, Wang S, Zhu Z (2006) Geopolymeric adsorbents from fly ash for dye removal from aqueous solution. J Colloid Interface Sci 30(1):52–59. Scholar
  51. 51.
    Mills A, Hazafy D, Parkinson J, Tuttle T, Hutchings MG (2011) Effect of alkali on methylene blue (C.I. Basic Blue 9) and other thiazine dyes. Dyes Pigm 88(2):149–155. Scholar
  52. 52.
    Barbosa TR, Foletto EL, Dotto GL, Jahn SL (2018) Preparation of mesoporous geopolymer using metakaolin and rice husk ash as synthesis precursors and its use as potential adsorbent to remove organic dye from aqueous solutions. Ceram Int 44:416–423. Scholar
  53. 53.
    Provis JL, Lukey GC, van Deventer JSJ (2005) Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results. Chem Mater 17:3075–3085. Scholar
  54. 54.
    Schmidt W (2012) Synthetic inorganic ion exchange materials. In: Inamuddin, Luqman M (eds) Ion exchange technology I. Theory and materials. Springer, pp 277–298Google Scholar
  55. 55.
    Bajpai PK (1986) Synthesis of mordenite type zeolite. Zeolites 6:2–8CrossRefGoogle Scholar
  56. 56.
    Querol Carceller X, Moreno N, Alastuey A, Juan Mainar R, Andres Gimeno JM, Lopez-Soler Á, Ayora C, Medinaceli A, Valero A (2007) Synthesis of high ion exchange zeolites from coal fly ash. Geologica Acta 5(1):49–57.
  57. 57.
    Franus W, Wdowin M, Franus M (2014) Synthesis and characterization of zeolites prepared from industrial fly ash. Environ Monit Assess 186:5721–5729. Scholar
  58. 58.
    Jha B (2016) Basics of zeolites. In: Jha B, Singh DN (eds) Fly ash zeolites: innovations, applications, and directions, advanced structured materials. Springer. Scholar
  59. 59.
    Van Jaarsveld JGS, Van Deventer JSJ, Schwartzman A (1999) The potential use of geopolymeric materials to immobilise toxic metals: part II. Material and leaching characteristics. Mineral Eng 12(1):75–91. Scholar
  60. 60.
    Van Jaarsveld JGS, Van Deventer JSJ (1999) The effect of metal contaminants on the formation and properties of waste-based geopolymers. Cem Concr Res 29:1189–1200. Scholar
  61. 61.
    Novais RM, Buruberri LH, Seabra MP, Labrincha JA (2016) Novel porous fly-ash containing geopolymer monoliths for lead adsorption from wastewaters. J Hazard Mater 318:631–640. Scholar
  62. 62.
    Buic Z, Zelić B (2009) Application of clay for petrochemical wastewater pretreatment. Water Qual Res J Can 44:399–406CrossRefGoogle Scholar
  63. 63.
    Nasef MM, Ujang Z (2012) Introduction to ion exchange processes. In: Inamuddin, Luqman M (eds) Ion exchange technology I. Theory and materials. Springer, pp 1–40Google Scholar
  64. 64.
    Margeta K, Logar NZ, Šiljeg M, Farkas A (2013) Natural zeolites in water treatment—how effective is their use, water treatment. In: Dr. Elshorbagy W (ed) InTech. Available from: Scholar
  65. 65.
    Katsou E, Malamis S, Tzanoudaki M, Haralambous KJ, Loizidou M (2011) Regeneration of natural zeolite polluted by lead and zinc in wastewater treatment systems. J Hazard Mater 189(3):773–786. Scholar
  66. 66.
    Cincotti A, Mameli A, Locci AM, Orrù R, Cao G (2006) Heavy metals uptake by Sardinian natural zeolites: experiment and modeling. Ind Eng Chem Res 45(3):1074–1084. Scholar
  67. 67.
    Sprynskyy M, Buszewski B, Terzyk AP, Namieśnik J (2006) Study of the selection mechanism of heavy metal (Pb2 + , Cu2 + , Ni2 + , and Cd2 +) adsorption on clinoptilolite. J Colloid Interface Sci 304(1):21–28. Scholar
  68. 68.
    Zhou CF, Zhu JH (2005) Adsorption of nitrosamines in acidic solution by zeolites. Chemosphere 58(1):109–114. Scholar
  69. 69.
    Abora K, Beleña I, Bernal SA, Dunster A, Nixon PA, Provis JL, Tagnit-Hamou A, Winnefeld F (2014) Durability and testing—chemical matrix degradation processes. In: Provis JL, van Devente JSJ (eds) Alkali activated materials: state-of-the-art report, RILEM TC 224-AAM. Springer, pp 177–221Google Scholar
  70. 70.
    Li Q, Sun Z, Tao D, Xu Y, Li P, Cui H, Zhai J (2013) Immobilization of simulated radionuclide 133Cs + by fly ash-based geopolymer. J Hazard Mater 262:325–331. Scholar
  71. 71.
    Bernal SA, Krivenko PV, Provis JL, Puertas F, Rickard WDA, Shi C, Van Riessen A (2014) Other potential applications for alkali-activated materials. In: Provis JL, van Devente JSJ (eds) Alkali Activated materials: state-of-the-art report, RILEM TC 224-AAM. Springer, pp 339–379Google Scholar
  72. 72.
    Hizal J, Tutem E, Guclu K, Hugul M, Ayhan S, Apak R, Kilinckale F (2013) Heavy metal removal from water by red mud and coal fly ash: an integrated adsorption–solidification/stabilization process. Desalin Water Treat 51:7181–7193. Scholar
  73. 73.
    Ipatti A (1992) Solidification of ion-exchange resins with alkali-activated blast-furnace slag. Cem Concr Res 22:281–286. Scholar
  74. 74.
    Kuenzel C, Cisneros JF, Neville TP, Vandeperre LJ, Simons SJR, Bensted J, Cheeseman CR (2015) Encapsulation of Cs/Sr contaminated clinoptilolite in geopolymers produced from metakaolin. J Nucl Mater 466:94–99. Scholar
  75. 75.
    Ferone C, Roviello G, Colangelo F, Cioffi R, Tarallo O (2013) Novel hybrid organic-geopolymer materials. Appl Clay Sci 73:42–50. Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Zarqa CollegeAl-Balqa Applied UniversityZarqaJordan

Personalised recommendations