Environmental Science and Pollution Research

, Volume 25, Issue 34, pp 34550–34558 | Cite as

Molecular design of macrocyclic compounds for complete removal of thallium(I) from wastewater

  • Zhuo ZhaoEmail author
  • Huan Tian
  • Menglong Zhang
  • Yongxiang Yang
  • Hongliang Zhang
Research Article


Design of new adsorbents for complete removal of thallium(I) from wastewater is of significant importance. Based on the theory of binding ability between crown ether and metal ion, a kind of Tl(I)-selected crown ether, thio-18-crown-6 ether, was designed. Subsequently, modeling calculations were performed to investigate the microscopic interaction between 18-crown-6 ether and its sulfur-substituted derivatives with Tl+. The results showed that thio-18-crown-6 ether generally showed higher affinity to Tl+ than 18-crown-6. The stabilities of these complexes ranked in an order of 5S-18C6 > 4S-18C6(II) > 2S-18C6(I) > 2S-18C6(II) > 6S-18C6 > 3S-18C6 > 18C6 > 1S-18C6. The binding energies of 5S-18C6 with free Zn2+, Pb2+, Cu2+, and Cd2+, which are usually impurity ions in thallium-containing wastewater, were more negative than with Tl+, indicating more affinity of 5S-18C6 toward these free two-valence ions. However, after the influence of solvent (water) was taken into account, 5S-18C6 showed fairly high selectivity to Tl(I) over Zn2+, Pb2+, Cu2+, and Cd2+. Therefore, 5S-18C6 should be a proper compound which has the promising potential to be adopted for the complete and selective removal of Tl(I) from wastewater. Further synthesis and adsorption experiments are needed to verify this prediction.


Molecular design Thallium Removal Molecular modeling calculation Wastewater 


Funding information

This work was supported by the National Natural Science Foundation of China (51574003, U1703130, 51704011).


  1. Ali SM, Maity DK, De S, Shenoi MRK (2008) Ligands for selective metal ion extraction: a molecular modeling approach. Desalination 232(1–3):181–190CrossRefGoogle Scholar
  2. Al-Kahtani A, Al-Jallal N, El-Azhary A (2014) Conformational and vibrational analysis of 18-crown-6–alkali metal cation complexes. Spectrochim Acta A Mol Biomol Spectrosc 132:70–83CrossRefGoogle Scholar
  3. Antón MAL, Spears DA, Somoano MD, Tarazona MRM (2013) Thallium in coal: analysis and environmental implications. Fuel 105(7):13–18CrossRefGoogle Scholar
  4. Bajaj AV, Poonia NS (1988) Comprehensive coordination chemistry of alkali and alkaline earth cations with macrocyclic multidentates: latest position. Coord Chem Rev 87:55–213CrossRefGoogle Scholar
  5. Cooper TE, Armentrout PB (2010) Threshold collision-induced dissociation of hydrated cadmium (II): experimental and theoretical investigation of the binding energies for Cd2+(H2O)n complexes (n = 4–11). Chem Phys Lett 486:1–3): 1-6CrossRefGoogle Scholar
  6. Dashti Khavidaki H, Aghaie H (2013) Adsorption of thallium (I) ions using eucalyptus leaves powder. CLEAN–Soil Air Water 41(7):673–679CrossRefGoogle Scholar
  7. Diao KS, Wang HJ (2009) The nitrogen position effect on the selectivity of diazacrown ethers to metal ion. J Mol Struct Theochem 910(1):163–168CrossRefGoogle Scholar
  8. Díaz N, Suárez D, Merz KM Jr (2000) Hydration of zinc ions: theoretical study of [Zn(H2O)4](H2O)8 2+ and [Zn(H2O)6](H2O)6 2+. Chem Phys Lett 326(3–4):288–292CrossRefGoogle Scholar
  9. Dunitz JD, Dobler M, Seiler P, Phizackerley RP (1974) Crystal structure analyses of 1,4,7,10,13,16-hexaoxacyclooctadecane and its complexes with alkali thiocyanates. Acta Crystallogr B 30(11):2733–2738CrossRefGoogle Scholar
  10. Ganesan P, Kamaraj R, Sozhan G, Vasudevan S (2013) Oxidized multiwalled carbon nanotubes as adsorbent for the removal of manganese from aqueous solution. Environ Sci Pollut Res 20(2):987–996CrossRefGoogle Scholar
  11. Hazra DK et al (2013) 18-Crown-6 ether templated transition-metal dicyanamido complexes: synthesis, structural characterization and DFT studies. J Mol Struct 1033(1033):137–144CrossRefGoogle Scholar
  12. Izatt RM, Bradshaw JS, Nielsen SA, Lamb JD, Christensen JJ, Sen D (1985) Thermodynamic and kinetic data for cation-macrocycle interaction. Chem Rev 85(4):271–339CrossRefGoogle Scholar
  13. Izatt RM, Pawlak K, Bradshaw JS, Bruening RL (1991) Thermodynamic and kinetic data for macrocycle interactions with cations and anions. Chem Rev 91(8):1721–2085CrossRefGoogle Scholar
  14. Izatt SR, Bruening RL, Izatt NE (2012) Metal separations and recovery in the mining industry. JOM 64(11):1279–1284CrossRefGoogle Scholar
  15. Izatt RM, Izatt SR, Izatt NE, Krakowiak KE, Bruening RL, Navarro L (2015) Industrial applications of molecular recognition technology to separations of platinum group metals and selective removal of metal impurities from process streams. Green Chem 17(4):2236–2245CrossRefGoogle Scholar
  16. Jabbari A, Hasani M, Shamsipur M (1993) Conductance study of complex formation of thallium and silver ions with several crown ethers in acetonitrile, acetone and dimethylformamide solutions. J Incl Phenom Mol Recognit Chem 15(4):329–340CrossRefGoogle Scholar
  17. Lee AG (1972) The coordination chemistry of thallium(I). Coord Chem Rev 8(4):289–349CrossRefGoogle Scholar
  18. Liu W, Zhang P, Borthwick AG, Chen H, Ni J (2014) Adsorption mechanisms of thallium (I) and thallium (III) by titanate nanotubes: ion-exchange and co-precipitation. J Colloid Interface Sci 423:67–75CrossRefGoogle Scholar
  19. Maeda T, Kimura K (1979) Solvent extraction of silver and thallium picrates with poly- and bis-(crown ether)s. Anal Bioanal Chem 298(5):363–366Google Scholar
  20. Maeda T, Kimura K, Shono T (1979) Solvent extraction of silver and thallium picrates with poly-and bis-(crown ether) s. Fresenius’ Z Anal Chem 298(5):363–366CrossRefGoogle Scholar
  21. Minami C, Takei K, Funahashi T, Kubota H (1990) Recovery of high purity thallium at Sumitomo Harima Works, Rare metals 1990 Kokura, Kelakyushu, Japan, pp. 259–262Google Scholar
  22. Pedersen CJ (1967) Cyclic polyethers and their complexes with metal salts. J Am Chem Soc 89(26):7017–7036CrossRefGoogle Scholar
  23. Ramakrishnan K, Aarthi P, Soundararajan J, Mu N, Subramanyan V (2016) Kinetics, thermodynamics and isotherm modeling for removal of nitrate from liquids by facile one-pot electrosynthesized nano zinc hydroxide. J Mol Liquids 216:204–211Google Scholar
  24. Sangvanich T, Sukwarotwat V, Wiacek RJ, Grudzien RM, Fryxell GE, Addleman RS, Timchalk C, Yantasee W (2010) Selective capture of cesium and thallium from natural waters and simulated wastes with copper ferrocyanide functionalized mesoporous silica. J Hazard Mater 182(1):225–231CrossRefGoogle Scholar
  25. Sato T, Sato K (1992) Liquid-liquid extraction of indium (III) from aqueous acid solutions by acid organophosphorus compounds. Hydrometallurgy 30(1–3):367–383CrossRefGoogle Scholar
  26. Shamsipur M, Rounaghi G, Popov AI (1980) Sodium-23, cesium-133 and thallium-205 NMR study of sodium, cesium and thallium complexes with large crown ethers in nonaqueous solutions. J Solut Chem 9(9):701–714CrossRefGoogle Scholar
  27. Tamura H, Kimura K, Shono T (1980) Thallium (I)-selective PVC membrane electrodes based on bis (crown ether) s. J Electroanal Chem Interfacial Electrochem 115(1):115–121CrossRefGoogle Scholar
  28. Tatsi K, Turner A (2014) Distributions and concentrations of thallium in surface waters of a region impacted by historical metal mining (Cornwall, UK). Sci Total Environ 473:139–146CrossRefGoogle Scholar
  29. Twidwell LG, Williams-Beam C (2002) Potential technologies for removing thallium from mine and process wastewater: an annotation of the literature. Eur J Miner Process Environ Prot 2(1):1–10Google Scholar
  30. Vasudevan S, Lakshmi J (2012) Process conditions and kinetics for the removal of copper from water by electrocoagulation. Environ Eng Sci 29(7):563–572CrossRefGoogle Scholar
  31. Velghe F (1977) The co-ordination of hydrated Cu(II)- and Ni(II)-ions on montmorillonite surface. Clays Clay Miner 25(6):375–380CrossRefGoogle Scholar
  32. Vincent T, Taulemesse JM, Dauvergne A, Chanut T, Testa F, Guibal E (2014) Thallium (I) sorption using Prussian blue immobilized in alginate capsules. Carbohydr Polym 99:517–526CrossRefGoogle Scholar
  33. Wan S, Ma M, Lv L, Qian L, Xu S, Xue Y, Ma Z (2014) Selective capture of thallium (I) ion from aqueous solutions by amorphous hydrous manganese dioxide. Chem Eng J 239:200–206CrossRefGoogle Scholar
  34. Wen L, Pan Z, Borthwick AGL, Hao C, Jinren N (2014) Adsorption mechanisms of thallium(I) and thallium(III) by titanate nanotubes: ion-exchange and co-precipitation. J Colloid Interface Sci 423(6):67–75Google Scholar
  35. Xiao T, Yang F, Li S, Zheng B, Ning Z (2012) Thallium pollution in China: a geo-environmental perspective. Sci Total Environ 421:51–58CrossRefGoogle Scholar
  36. Yantasee W, Warner CL, Sangvanich T, Addleman RS, Carter TG, Wiacek RJ, Fryxell GE, Timchalk C, Warner MG (2007) Removal of heavy metals from aqueous systems with thiol functionalized superparamagnetic nanoparticles. Environ Sci Technol 41(14):5114–5119CrossRefGoogle Scholar
  37. Zitko V (1975) Toxicity and pollution potential of thallium. Sci Total Environ 4(2):185–192CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Zhuo Zhao
    • 1
    Email author
  • Huan Tian
    • 1
  • Menglong Zhang
    • 1
  • Yongxiang Yang
    • 2
  • Hongliang Zhang
    • 3
  1. 1.School of Metallurgical EngineeringAnhui University of TechnologyMaanshanPeople’s Republic of China
  2. 2.Department of Materials Science and EngineeringDelft University of TechnologyDelftthe Netherlands
  3. 3.School of Metallurgy and EnvironmentCentral South UniversityChangshaPeople’s Republic of China

Personalised recommendations