Adsorption of Cu(II) in aqueous solution using microwave-assisted titanate nanotubes

  • Lin-Han Chiang Hsieh
  • Hsin-Hung Ou
  • Chao-Wei HuangEmail author
Original Article


This study aims to investigate the adsorption behavior and mechanism of Cu(II) over microwave-assisted titanate nanotubes (MTNTs, NaxH2−xTi3O7). The effect of power level of microwave irradiation during MTNT synthesis on the adsorption mechanism is also examined. Regarding the adsorption potential of Cu(II) over MTNTs, more than 80% of Cu(II) is removed within the first minute, and the adsorption equilibrium is reached by half an hour. The adsorption capacities of MTNTs obtained from Langmuir model fall in the range of 1.86–2.46 mmol g−1. According to the characterizations including ICP–AES, XRD, FT–IR/DRIFT, XPS, and H2-TPR, the amount and binding intensity of intercalated Na+ within MTNTs, which are greatly dependent upon the power level of microwave irradiation during MTNT synthesis, dominate the adsorption kinetics, the adsorption capability, the adsorption stabilization, and the extent of copper complexation. An adsorption mechanism is also proposed such that ion exchange process and complexation reaction are both involved in the Cu(II) adsorption over MTNTs.


Copper ion adsorption Titanate nanotubes Kinetic model Microwave-assisted 


Supplementary material

13204_2018_932_MOESM1_ESM.doc (160 kb)
Supplementary material 1 (DOC 160 KB)


  1. An H-Q, Zhu B-L, Wu H-Y, Zhang M, Wang S-R, Zhang S-M et al (2008) Synthesis and characterization of titanate and CS2-modified titanate nanotubes as well as their adsorption capacities for heavy metal ions. Chem J Chin Univ 3:000Google Scholar
  2. Bavykin D-V, Walsh F-C (2007) Kinetics of alkali metal ion exchange into nanotubular and nanofibrous titanates. J Phys Chem C 111:14644–14651CrossRefGoogle Scholar
  3. Bavykin D-V, Lapkin A-A, Plucinski P-K, Torrente-Murciano L, Friedrich J-M, Walsh F-C (2006) Deposition of Pt, Pd, Ru and Au on the surfaces of titanate nanotubes. Top Catal 39:151–160CrossRefGoogle Scholar
  4. Capasso R, Pigna M, De Martino A, Pucci M, Sannino F, Violante A (2004) Potential remediation of waters contaminated with Cr (III), Cu, and Zn by sorption on the organic polymeric fraction of olive mill wastewater (polymerin) and its derivatives. Environ Sci Technol 38:5170–5176CrossRefGoogle Scholar
  5. Chen Q, Zhou W, Du G-H, Peng L-M (2002a) Trititanate nanotubes made via a single alkali treatment. Adv Mater 14:1208–1211CrossRefGoogle Scholar
  6. Chen Q, Du G, Zhang S, Peng L-M (2002b) The structure of trititanate nanotubes. Acta Crystallogr Sect B 58:587–593CrossRefGoogle Scholar
  7. Colon G, Maicu M, Hidalgo MS, Navio J (2006) Cu-doped TiO2 systems with improved photocatalytic activity. Appl Catal B 67:41–51CrossRefGoogle Scholar
  8. Du A-J, Sun D-D, Leckie J-O (2011) Selective sorption of divalent cations using a high capacity sorbent. J Hazard Mater 187:96–100CrossRefGoogle Scholar
  9. EL-Hefnawy M-E, Selim E-M, Assaad F-F, Ismail A-I (2014) The effect of chloride and sulfate ions on the adsorption of Cd2+ on clay and sandy loam Egyptian soils. Sci World J 2014:806252. CrossRefGoogle Scholar
  10. Hsieh C-H, Lo S-L, Kuan W-H, Chen C-L (2006) Adsorption of copper ions onto microwave stabilized heavy metal sludge. J Hazard Mater 136:338–344CrossRefGoogle Scholar
  11. Idakiev V, Yuan Z-Y, Tabakova T, Su B-L (2005) Titanium oxide nanotubes as supports of nano-sized gold catalysts for low temperature water-gas shift reaction. Appl Catal A 281:149–155CrossRefGoogle Scholar
  12. Jin Q, Yang Y, Dong X, Fang J (2016) Site energy distribution analysis of Cu (II) adsorption on sediments and residues by sequential extraction method. Environ Pollut 208:450–457CrossRefGoogle Scholar
  13. Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1998) Formation of titanium oxide nanotube. Langmuir 14:3160–3163CrossRefGoogle Scholar
  14. Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1999) Titania nanotubes prepared by chemical processing. Adv Mater 11:1307–1311CrossRefGoogle Scholar
  15. Kim M-S, Hong K-M, Chung J-G (2003) Removal of Cu (II) from aqueous solutions by adsorption process with anatase-type titanium dioxide. Water Res 37:3524–3529CrossRefGoogle Scholar
  16. Lee C-K, Liu S-S, Juang L-C, Wang C-C, Lyu M-D, Hung S-H (2007) Application of titanate nanotubes for dyes adsorptive removal from aqueous solution. J Hazard Mater 148:756–760CrossRefGoogle Scholar
  17. Lim S-F, Zheng Y-M, Zou S-W, Chen J-P (2008) Characterization of copper adsorption onto an alginate encapsulated magnetic sorbent by a combined FT-IR, XPS, and mathematical modeling study. Environ Sci Technol 42:2551–2556CrossRefGoogle Scholar
  18. Lin C-J, Lo S-L, Liou Y-H (2005) Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin. Chemosphere 59:1299–1307CrossRefGoogle Scholar
  19. Liu S-S, Lee C-K, Chen H-C, Wang C-C, Juang L-C (2009) Application of titanate nanotubes for Cu (II) ions adsorptive removal from aqueous solution. Chem Eng J 147:188–193CrossRefGoogle Scholar
  20. Liu W, Wang T, Borthwick AG, Wang Y, Yin X, Li X et al (2013a) Adsorption of Pb2+, Cd2+, Cu2+ and Cr3+ onto titanate nanotubes: competition and effect of inorganic ions. Sci Total Environ 456:171–180CrossRefGoogle Scholar
  21. Liu W, Chen H, Borthwick AG, Han Y, Ni J (2013b) Mutual promotion mechanism for adsorption of coexisting Cr (III) and Cr (VI) onto titanate nanotubes. Chem Eng J 232:228–236CrossRefGoogle Scholar
  22. Liu W, Sun W, Han Y, Ahmad M, Ni J (2014a) Adsorption of Cu (II) and Cd (II) on titanate nanomaterials synthesized via hydrothermal method under different NaOH concentrations: role of sodium content. Colloids Surf A 452:138–147CrossRefGoogle Scholar
  23. Liu W, Zhang P, Borthwick AG, Chen H, Ni J (2014b) Adsorption mechanisms of thallium (I) and thallium (III) by titanate nanotubes: ion-exchange and co-precipitation. J Colloid Interface Sci 423:67–75CrossRefGoogle Scholar
  24. Liu W, Zhao X, Wang T, Zhao D, Ni J (2016) Adsorption of U (VI) by multilayer titanate nanotubes: effects of inorganic cations, carbonate and natural organic matter. Chem Eng J 286:427–435CrossRefGoogle Scholar
  25. Ma R, Sasaki T, Bando Y. Alkali metal cation intercalation properties of titanate nanotubes. Chem Commun. 2005:948–950Google Scholar
  26. Nian J-N, Chen S-A, Tsai C-C, Teng H (2006) Structural feature and catalytic performance of Cu species distributed over TiO2 nanotubes. J Phys Chem B 110:25817–25824CrossRefGoogle Scholar
  27. Ou H-H, Lo S-L (2007) Effect of Pt/Pd-doped TiO2 on the photocatalytic degradation of trichloroethylene. J Mol Catal A Chem 275:200–205CrossRefGoogle Scholar
  28. Ou H-H, Lo S-L, Liou Y-H (2007) Microwave-induced titanate nanotubes and the corresponding behaviour after thermal treatment. Nanotechnology 18:175702CrossRefGoogle Scholar
  29. Ou H-H, Liao C-H, Liou Y-H, Hong J-H, Lo S-L (2008) Photocatalytic oxidation of aqueous ammonia over microwave-induced titanate nanotubes. Environ Sci Technol 42:4507–4512CrossRefGoogle Scholar
  30. Ou H-H, Lo S-L, Liao C-H (2011) N-doped TiO2 prepared from microwave-assisted titanate nanotubes (NaxH2−x Ti3O7): the effect of microwave irradiation during TNT synthesis on the visible light photoactivity of N-Doped TiO2. J Phys Chem C 115:4000–4007CrossRefGoogle Scholar
  31. Sheng G, Hu B (2013) Role of solution chemistry on the trapping of radionuclide Th (IV) using titanate nanotubes as an efficient adsorbent. J Radioanal Nucl Chem 298:455–464CrossRefGoogle Scholar
  32. Sheng G, Dong H, Shen R, Li Y (2013) Microscopic insights into the temperature-dependent adsorption of Eu (III) onto titanate nanotubes studied by FTIR, XPS, XAFS and batch technique. Chem Eng J 217:486–494CrossRefGoogle Scholar
  33. Sheng G, Ye L, Li Y, Dong H, Li H, Gao X et al (2014) EXAFS study of the interfacial interaction of nickel (II) on titanate nanotubes: role of contact time, pH and humic substances. Chem Eng J 248:71–78CrossRefGoogle Scholar
  34. Sheng G, Linghu W, Chen Z, Xu D, Alsaedi A, Shammakh W et al (2016) Sequestration of selenate and selenite onto titanate nanotube: a combined classical batch and advanced EXAFS approach. Environ Nanotechnol Monit Manag 6:152–158Google Scholar
  35. Suetake J, Nosaka A-Y, Hodouchi K, Matsubara H, Nosaka Y (2008) Characteristics of titanate nanotube and the states of the confined sodium ions. J Phys Chem C 112:18474–18482CrossRefGoogle Scholar
  36. Sun X, Li Y (2003) Synthesis and characterization of ion-exchangeable titanate nanotubes. Chem Eur J 9:2229–2238CrossRefGoogle Scholar
  37. Tsai C-C, Teng H (2006) Structural features of nanotubes synthesized from NaOH treatment on TiO2 with different post-treatments. Chem Mater 18:367–373CrossRefGoogle Scholar
  38. Umek P, Cevc P, Jesih A, Gloter A, Ewels C-P, Arčon D (2005) Impact of structure and morphology on gas adsorption of titanate-based nanotubes and nanoribbons. Chem Mater 17:5945–5950CrossRefGoogle Scholar
  39. Umek P, Pregelj M, Gloter A, Cevc P, Jaglicic Z, Cˇeh M et al (2008) Coordination of intercalated Cu2+ sites in copper doped sodium titanate nanotubes and nanoribbons. J Phys Chem C 112:15311–15319CrossRefGoogle Scholar
  40. Viana B-C, Ferreira O-P, Souza Filho A-G, Rodrigues C-M, Moraes S-G, Mendes Filho J et al (2009) Decorating titanate nanotubes with CeO2 nanoparticles. J Phys Chem C 113:20234–20239CrossRefGoogle Scholar
  41. Wang Y-J, Jia D-A, Sun R-J, Zhu H-W, Zhou D-M (2008) Adsorption and cosorption of tetracycline and copper (II) on montmorillonite as affected by solution pH. Environ Sci Technol 42:3254–3259CrossRefGoogle Scholar
  42. Wang T, Liu W, Xiong L, Xu N, Ni J (2013a) Influence of pH, ionic strength and humic acid on competitive adsorption of Pb (II), Cd (II) and Cr (III) onto titanate nanotubes. Chem Eng J 215:366–374CrossRefGoogle Scholar
  43. Wang T, Liu W, Xu N, Ni J (2013b) Adsorption and desorption of Cd (II) onto titanate nanotubes and efficient regeneration of tubular structures. J Hazard Mater 250:379–386CrossRefGoogle Scholar
  44. Wang L, Liu W, Wang T, Ni J (2013c) Highly efficient adsorption of Cr (VI) from aqueous solutions by amino-functionalized titanate nanotubes. Chem Eng J 225:153–163CrossRefGoogle Scholar
  45. Xiong L, Chen C, Chen Q, Ni J (2011) Adsorption of Pb (II) and Cd (II) from aqueous solutions using titanate nanotubes prepared via hydrothermal method. J Hazard Mater 189:741–748CrossRefGoogle Scholar
  46. Yu K-P, Yu W-Y, Kuo M-C, Liou Y-C, Chien S-H (2008) Pt/titania-nanotube: a potential catalyst for CO2 adsorption and hydrogenation. Appl Catal B 84:112–118CrossRefGoogle Scholar
  47. Zhang Y, Zhu C, Liu F, Yuan Y, Wu H, Li A. Effects of ionic strength on removal of toxic pollutants from aqueous media with multifarious adsorbents: a review. Sci Total Environ. 2018Google Scholar
  48. Zhu B, Zhang X, Wang S, Zhang S, Wu S, Huang W (2007) Synthesis and catalytic performance of TiO2 nanotubes-supported copper oxide for low-temperature CO oxidation. Microporous Mesoporous Mater 102:333–336CrossRefGoogle Scholar

Copyright information

© King Abdulaziz City for Science and Technology 2018

Authors and Affiliations

  1. 1.Department of Environmental EngineeringChung Yuan Christian UniversityTaoyuanTaiwan
  2. 2.New Materials Research and Development DepartmentChina Steel CorporationKaohsiungTaiwan
  3. 3.Department of Chemical and Materials EngineeringNational Kaohsiung University of Science and TechnologyKaohsiungTaiwan
  4. 4.Photo-SMART (Photo-Sensitive Material Advanced Research and Technology) CenterKaohsiungTaiwan

Personalised recommendations