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Low-price MnO2 loaded sepiolite for Cd2+ capture

  • Gang Zhang
  • LiBin Liu
  • Elenica Shiko
  • Yi Cheng
  • Rui Zhang
  • Zhaogang Zeng
  • Tieguang Zhao
  • Yefeng ZhouEmail author
  • Hongbo Chen
  • Yang Liu
  • Xiayi HuEmail author


Cadmium ion (Cd2+) is one of the harmful metal ions in the wastewater and has attracted much attention for its removal. The current study proposes a low-cost adsorbent MnO2-sepiolite to capture Cd2+ from the aqueous solutions. The structure of the new MnO2-sepiolite adsorbent was characterized by using nitrogen adsorption–desorption isotherm, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The effects of MnO2-loading, pH and contact time of cadmium solution with the adsorbent were investigated with respect to the adsorption performance of MnO2-sepiolite. The Sips model was used to estimate the maximum adsorption capacity for capturing Cd2+ and the obtained results demonstrated that it reached 114.75 mg/g at pH 6 and T = 298 K, placing it in the top three most efficient adsorbents reported. Additionally, the experimental adsorption kinetic data was found in good agreement with the Avrami kinetic model. The obtained results also suggest that the MnO2-sepiolite still shows a high Cd2+ removal efficiency even after four adsorption–desorption cycles. A comparison between the cost of the proposed MnO2-sepiolites and other reported adsorbents for removing Cd2+ is provided and the results indicate that MnO2-sepiolite could be a very promising cost-effective adsorbent.


Sepiolite MnO2 Cadmium ion Adsorption Kinetics 



The work was supported by National Natural Science Foundation of China (21506179, 21506181, 51608464), Hunan Province Science and Technology Project (2016JJ3113, 2016JJ5006, 2017JJ3291, 2018SK2027, 2018RS3088, 2019JJ40281), Research Foundation of Education Bureau of Hunan Province (17B255, 17B256), Hunan Key Laboratory of Environment Friendly Chemical Process Integration Technology, National & Local United Engineering Research Centre for Chemical Process Simulation and Intensification, National Department of Education Engineering Research Centre for Chemical Process Simulation, Optimization and Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization and Xiangtan Science and Technology Project, China Scholarship Council (201707230001).


  1. Afify, A.S., Hassan, M., Piumetti, M., Peter, I., Bonelli, B., Tulliani, J.M.: Elaboration and characterization of modified sepiolites and their humidity sensing features for environmental monitoring. Appl. Clay Sci. 115, 165–173 (2015). Google Scholar
  2. Bhattacharyya, K.G., Sen Gupta, S.: Influence of acid activation of kaolinite and montmorillonite on adsorptive removal of Cd(II) from water. Ind. Eng. Chem. Res. 46(11), 3734–3742 (2007). Google Scholar
  3. Borbély, G., Nagy, E.: Removal of zinc and nickel ions by complexation–membrane filtration process from industrial wastewater. Desalination 240(1), 218–226 (2009). Google Scholar
  4. Chen, M.A., Kocar, B.D.: Radium sorption to iron (hydr)oxides, pyrite, and montmorillonite: implications for mobility. Environ. Sci. Technol. 52(7), 4023–4030 (2018). Google Scholar
  5. Da̧browski, A., Hubicki, Z., Podkościelny, P., Robens, E.: Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method. Chemosphere 56(2), 91–106 (2004). Google Scholar
  6. Demirbaş, Ö., Alkan, M., Doğan, M., Turhan, Y., Namli, H., Turan, P.: Electrokinetic and adsorption properties of sepiolite modified by 3-aminopropyltriethoxysilane. J. Hazard. Mater. 149(3), 650–656 (2007). Google Scholar
  7. Doğan, M., Turhan, Y., Alkan, M., Namli, H., Turan, P., Demirbaş, Ö.: Functionalized sepiolite for heavy metal ions adsorption. Desalination 230(1), 248–268 (2008). Google Scholar
  8. Eren, E., Afsin, B., Onal, Y.: Removal of lead ions by acid activated and manganese oxide-coated bentonite. J. Hazard. Mater. 161(2), 677–685 (2009). Google Scholar
  9. Eren, E., Cubuk, O., Ciftci, H., Eren, B., Caglar, B.: Adsorption of basic dye from aqueous solutions by modified sepiolite: equilibrium, kinetics and thermodynamics study. Desalination 252(1), 88–96 (2010). Google Scholar
  10. Fan, H.J., Anderson, P.R.: Copper and cadmium removal by Mn oxide-coated granular activated carbon. Sep. Purif. Technol. 45(1), 61–67 (2005). Google Scholar
  11. Foo, K.Y., Hameed, B.H.: Insights into the modeling of adsorption isotherm systems. Chem. Eng. J. 156(1), 2–10 (2010). Google Scholar
  12. Freundlich, H.: Über die adsorption in lösungen. Z. Phys. Chem. 57, 385–470 (1906)Google Scholar
  13. Günay, A., Arslankaya, E., Tosun, İ.: Lead removal from aqueous solution by natural and pretreated clinoptilolite: adsorption equilibrium and kinetics. J. Hazard. Mater. 146(1), 362–371 (2007). Google Scholar
  14. Guo, X., Zhang, S., Shan, X.: Adsorption of metal ions on lignin. J. Hazard. Mater. 151(1), 134–142 (2008). Google Scholar
  15. Gurgel, L.V.A., Gil, L.F.: Adsorption of Cu(II), Cd(II) and Pb(II) from aqueous single metal solutions by succinylated twice-mercerized sugarcane bagasse functionalized with triethylenetetramine. Water Res. 43(18), 4479–4488 (2009). Google Scholar
  16. Ho, Y.S.: Citation review of Lagergren kinetic rate equation on adsorption reactions. Scientometrics 59(1), 171–177 (2004). Google Scholar
  17. Ho, Y.S.: Review of second-order models for adsorption systems. J. Hazard. Mater. 136(3), 681–689 (2006). Google Scholar
  18. Huang, R., Wang, B., Yang, B., Zheng, D., Zhang, Z.: Equilibrium, kinetic and thermodynamic studies of adsorption of Cd(II) from aqueous solution onto HACC–bentonite. Desalination 280(1), 297–304 (2011). Google Scholar
  19. Irani, M., Fan, M., Ismail, H., Tuwati, A., Dutcher, B., Russell, A.G.: Modified nanosepiolite as an inexpensive support of tetraethylenepentamine for CO2 sorption. Nano Energy 11, 235–246 (2015). Google Scholar
  20. Järup, L., Åkesson, A.: Current status of cadmium as an environmental health problem. Toxicol. Appl. Pharmacol. 238(3), 201–208 (2009). Google Scholar
  21. Kara, M., Yuzer, H., Sabah, E., Celik, M.S.: Adsorption of cobalt from aqueous solutions onto sepiolite. Water Res. 37(1), 224–232 (2003). Google Scholar
  22. Karnitz, O., Gurgel, L.V.A., de Melo, J.C.P., Botaro, V.R., Melo, T.M.S., de Freitas Gil, R.P., Gil, L.F.: Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse. Bioresour. Technol. 98(6), 1291–1297 (2007). Google Scholar
  23. Khan, Z., Kumar, P., Kabir ud, D.: Kinetics of the reduction of water-soluble colloidal MnO2 by ascorbic acid. J. Colloid Interface Sci. 290(1), 184–189 (2005). Google Scholar
  24. Kim, J., Kwak, S.Y.: Efficient and selective removal of heavy metals using microporous layered silicate AMH-3 as sorbent. Chem. Eng. J. 313, 975–982 (2017). Google Scholar
  25. Kolta, G.A., Kerim, F.M.A., Azim, A.A.A.: Infrared absorption spectra of some manganese dioxide modifications and their thermal products. Zeitschrift für anorganische und allgemeine Chemie 384(3), 260–266 (1971). Google Scholar
  26. Lan, L., Li, Q., Gu, G., Zhang, H., Liu, B.: Hydrothermal synthesis of γ-MnOOH nanorods and their conversion to MnO2, Mn2O3, and Mn3O4 nanorods. J. Alloy. Compd. 644, 430–437 (2015). Google Scholar
  27. Langmuir, I.: The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40(9), 1361–1403 (1918). Google Scholar
  28. Lazarević, S., Janković-Častvan, I., Potkonjak, B., Janaćković, D., Petrović, R.: Removal of Co2+ ions from aqueous solutions using iron-functionalized sepiolite. Chem. Eng. Process. 55, 40–47 (2012). Google Scholar
  29. Lee, Y., Um, I.-H., Yoon, J.: Arsenic(III) oxidation by iron(VI) (ferrate) and subsequent removal of arsenic(V) by iron(III) coagulation. Environ. Sci. Technol. 37(24), 5750–5756 (2003). Google Scholar
  30. Liang, X., Xu, Y., Sun, G., Wang, L., Sun, Y., Sun, Y., Qin, X.: Preparation and characterization of mercapto functionalized sepiolite and their application for sorption of lead and cadmium. Chem. Eng. J. 174(1), 436–444 (2011). Google Scholar
  31. Liu, L., Chen, H., Shiko, E., Fan, X., Zhou, Y., Zhang, G., Luo, X., Hu, X.: Low-cost DETA impregnation of acid-activated sepiolite for CO2 capture. Chem. Eng. J. 353, 940–948 (2018). Google Scholar
  32. Liu, P., Yuan, N., Xiong, W., Wu, H., Pan, D., Wu, W.: Removal of nickel(II) from aqueous solutions using synthesized β-zeolite and its ethylenediamine derivative. Ind. Eng. Chem. Res. 56(11), 3067–3076 (2017a). Google Scholar
  33. Liu, R., Wang, J., Zhang, J., Xie, S., Wang, X., Ji, Z.: Honeycomb-like micro-mesoporous structure TiO2/sepiolite composite for combined chemisorption and photocatalytic elimination of formaldehyde. Microporous Mesoporous Mater. 248, 234–245 (2017b). Google Scholar
  34. Lopes, E.C.N., dos Anjos, F.S.C., Vieira, E.F.S., Cestari, A.R.: An alternative Avrami equation to evaluate kinetic parameters of the interaction of Hg(II) with thin chitosan membranes. J. Colloid Interface Sci. 263(2), 542–547 (2003). Google Scholar
  35. Lu, J., Li, Y., Yin, M., Ma, X., Lin, S.: Removing heavy metal ions with continuous aluminum electrocoagulation: a study on back mixing and utilization rate of electro-generated Al ions. Chem. Eng. J. 267, 86–92 (2015). Google Scholar
  36. Ma, Y., Zhang, G.: Sepiolite nanofiber-supported platinum nanoparticle catalysts toward the catalytic oxidation of formaldehyde at ambient temperature: efficient and stable performance and mechanism. Chem. Eng. J. 288, 70–78 (2016). Google Scholar
  37. Maity, J., Ray, S.K.: Chitosan based nano composite adsorbent—synthesis, characterization and application for adsorption of binary mixtures of Pb(II) and Cd(II) from water. Carbohyd. Polym. 182, 159–171 (2018). Google Scholar
  38. Padilla-Ortega, E., Leyva-Ramos, R., Flores-Cano, J.V.: Binary adsorption of heavy metals from aqueous solution onto natural clays. Chem. Eng. J. 225, 535–546 (2013). Google Scholar
  39. Pawar, R.R., Lalhmunsiama, Kim, M., Kim, J.-G., Hong, S.-M., Sawant, S.Y., Lee, S.M.: Efficient removal of hazardous lead, cadmium, and arsenic from aqueous environment by iron oxide modified clay-activated carbon composite beads. Appl. Clay Sci. 162, 339–350 (2018). Google Scholar
  40. Rodríguez, A., Ovejero, G., Mestanza, M., García, J.: Removal of dyes from wastewaters by adsorption on sepiolite and pansil. Ind. Eng. Chem. Res. 49(7), 3207–3216 (2010). Google Scholar
  41. Sarı, A., Şahinoğlu, G., Tüzen, M.: Antimony(III) adsorption from aqueous solution using raw perlite and Mn-modified perlite: equilibrium, thermodynamic, and kinetic studies. Ind. Eng. Chem. Res. 51(19), 6877–6886 (2012). Google Scholar
  42. Sari, A., Tuzen, M.: Cd(II) adsorption from aqueous solution by raw and modified kaolinite. Appl. Clay Sci. 88–89, 63–72 (2014). Google Scholar
  43. Sarı, A., Tuzen, M.: Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste. Desalination 249(1), 260–266 (2009). Google Scholar
  44. Sen Gupta, S., Bhattacharyya, K.G.: Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium. J. Environ. Manage. 87(1), 46–58 (2008). Google Scholar
  45. Shirvani, M., Kalbasi, M., Shariatmadari, H., Nourbakhsh, F., Najafi, B.: Sorption–desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis. Chemosphere 65(11), 2178–2184 (2006). Google Scholar
  46. Sips, R.: Combined form of Langmuir and Freundlich equations. J. Chem. Phys. 33, 490–495 (1948)Google Scholar
  47. Sutirman, Z.A., Sanagi, M.M., Abd Karim, K.J., Wan Ibrahim, W.A., Jume, B.H.: Equilibrium, kinetic and mechanism studies of Cu(II) and Cd(II) ions adsorption by modified chitosan beads. Int. J. Biol. Macromol. 116, 255–263 (2018). Google Scholar
  48. Uddin, M.K.: A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade. Chem. Eng. J. 308, 438–462 (2017). Google Scholar
  49. Verma, V.K., Tewari, S., Rai, J.P.N.: Ion exchange during heavy metal bio-sorption from aqueous solution by dried biomass of macrophytes. Biores. Technol. 99(6), 1932–1938 (2008). Google Scholar
  50. Violante, A., Gaudio, S.D., Pigna, M., Ricciardella, M., Banerjee, D.: Coprecipitation of arsenate with metal oxides. 2. Nature, mineralogy, and reactivity of iron(III) precipitates. Environ. Sci. Technol. 41(24), 8275–8280 (2007). Google Scholar
  51. Wang, B., Chang, Y.-H., Zhi, L.J.: High yield production of graphene and its improved property in detecting heavy metal ions. New Carbon Mater. 26(1), 31–35 (2011). Google Scholar
  52. Wang, H., Gao, B., Wang, S., Fang, J., Xue, Y., Yang, K.: Removal of Pb(II), Cu(II), and Cd(II) from aqueous solutions by biochar derived from KMnO4 treated hickory wood. Bioresour. Technol. 197, 356–362 (2015). Google Scholar
  53. Wang, Q., Zheng, C., Shen, Z., Lu, Q., He, C., Zhang, T.C., Liu, J.: Polyethyleneimine and carbon disulfide co-modified alkaline lignin for removal of Pb2 + ions from water. Chem. Eng. J. 359, 265–274 (2019). Google Scholar
  54. Xu, H., Jia, J., Guo, Y., Qu, Z., Liao, Y., Xie, J., Shangguan, W., Yan, N.: Design of 3D MnO2/carbon sphere composite for the catalytic oxidation and adsorption of elemental mercury. J. Hazard. Mater. 342, 69–76 (2018). Google Scholar
  55. Xu, R., Zhou, G., Tang, Y., Chu, L., Liu, C., Zeng, Z., Luo, S.: New double network hydrogel adsorbent: highly efficient removal of Cd(II) and Mn(II) ions in aqueous solution. Chem. Eng. J. 275, 179–188 (2015). Google Scholar
  56. Zhang, H., Dang, Q., Liu, C., Cha, D., Yu, Z., Zhu, W., Fan, B.: Uptake of Pb(ii) and Cd(ii) on chitosan microsphere surface successively grafted by methyl acrylate and diethylenetriamine. ACS Appl. Mater. Interfaces. 9(12), 11144–11155 (2017). Google Scholar
  57. Zhao, G., Li, J., Ren, X., Chen, C., Wang, X.: Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management. Environ. Sci. Technol. 45(24), 10454–10462 (2011). Google Scholar
  58. Zhou, F., Yan, C., Zhang, Y., Tan, J., Wang, H., Zhou, S., Pu, S.: Purification and defibering of a Chinese sepiolite. Appl. Clay Sci. 124–125, 119–126 (2016). Google Scholar
  59. Zhuang, G., Gao, J., Chen, H., Zhang, Z.: A new one-step method for physical purification and organic modification of sepiolite. Appl. Clay Sci. 153, 1–8 (2018). Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Chemical EngineeringXiangtan UniversityXiangtanPeople’s Republic of China
  2. 2.Department of Chemical EngineeringUniversity of BathBathUK
  3. 3.Xiangtan Sepiolite Technology Co., LtdXiangtanPeople’s Republic of China
  4. 4.Hunan Jufa Technology Co., LtdXiangtanPeople’s Republic of China
  5. 5.Hunan BG Well-point Environmental Science & Technology Co., LtdChangshaPeople’s Republic of China
  6. 6.School of Engineering, Institute for Materials and ProcessesUniversity of EdinburghEdinburghUK

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