Fabrication of Carbonaceous-Modified Halloysite Nanotubes for the Removal of Metal Ions from Aqueous Solution

Abstract

Halloysite nanotube-carbonaceous (HNT-C) composites were fabricated through one-pot hydrothermal carbonization of fructose and sodium carboxymethyl cellulose for use as an adsorbent for the removal of Pb(II), Zn(II), and Cu(II) from wastewater. The composites were chemically treated with sulfuric acid after carbonization. The acidic treatment of HNT-C structures contributed to a larger specific surface area and surface functionality, which was favorable for adsorbing more metal ions. Carbonaceous-modified HNTs were characterized by elemental analysis, FT IR, XRD, and BET analysis. Metal ion adsorption experiments were conducted with solutions containing low and high total metal ion concentrations (Cu, Zn, Pb) by mixing with HNT-C composites at a solid/liquid ratio of 1.0 and 10.0 g/L. The results indicated that the HNT C composites exhibited promising Zn(II) adsorption up to 94%, while no Zn(II) adsorbed onto unmodified HNTs. The amount of Pb(II), Zn(II), and Cu(II) ions that were taken up increased as the amount of adsorbent was increased up to 10 g/L in an aqueous solution. The HNT-C composites exhibited the highest adsorption efficiency for Pb(II) ions.

Keywords

• adsorbent
• adsorption
• halloysite nanotube
• heavy metal
• wastewater

References

1. 1. Sönmez AY, Hisar O, Karataş M, Arslan G, Aras MS. Sular Bilgisi. 2nd edition. Ankara: Nobel Yayın Dağıtım A.Ş.; 2008.
2. 2. Sankhla MS, Kumari M, Nandan M, Kumar R, Agrawal P. Heavy Metals Contamination in Water and their Hazardous Effect on Human Health-A Review. Int J Curr Microbiol Appl Sci [Internet]. 2016 Oct 15;5(10):759–66. Available from: .
3. 3. World Healthy Organization (WHO). Guidelines for drinking-water quality: recommendations. World Healthy Organization; 2004.
4. 4. Allalou S, Kheribet R, Benmounah A. Effects of calcined halloysite nano-clay on the mechanical properties and microstructure of low-clinker cement mortar. Case Stud Constr Mater [Internet]. 2019 Jun 1;10:e00213. Available from: .
5. 5. Kiani G. High removal capacity of silver ions from aqueous solution onto Halloysite nanotubes. Appl Clay Sci [Internet]. 2014 Mar 1;90:159–64. Available from: .
6. 6. Cataldo S, Lazzara G, Massaro M, Muratore N, Pettignano A, Riela S. Functionalized halloysite nanotubes for enhanced removal of lead(II) ions from aqueous solutions. Appl Clay Sci [Internet]. 2018 May 1;156:87–95. Available from: .
7. 7. Hermawan AA, Chang JW, Pasbakhsh P, Hart F, Talei A. Halloysite nanotubes as a fine grained material for heavy metal ions removal in tropical biofiltration systems. Appl Clay Sci [Internet]. 2018 Aug 1;160:106–15. Available from: .
8. 8. Luo P, Zhang J, Zhang B, Wang J, Zhao Y, Liu J. Preparation and Characterization of Silane Coupling Agent Modified Halloysite for Cr(VI) Removal. Ind Eng Chem Res [Internet]. 2011 Sep 7;50(17):10246–52. Available from: .

9. 9. Yu L, Wang H, Zhang Y, Zhang B, Liu J. Recent advances in halloysite nanotube derived composites for water treatment. Environ Sci Nano [Internet]. 2016 Feb 11;3(1):28–44. Available from: .
10. 10. Jiang L, Zhang C, Wei J, Tjiu W, Pan J, Chen Y, et al. Surface modifications of halloysite nanotubes with superparamagnetic Fe3O4 nanoparticles and carbonaceous layers for efficient adsorption of dyes in water treatment. Chem Res Chinese Univ [Internet]. 2014 Dec 18;30(6):971–7. Available from: .
11. 11. Tharmavaram M, Pandey G, Rawtani D. Surface modified halloysite nanotubes: A flexible interface for biological, environmental and catalytic applications. Adv Colloid Interface Sci [Internet]. 2018 Nov 1;261:82–101. Available from: .
12. 12. Maziarz P, Prokop A, Matusik J. A comparative study on the removal of Pb(II), Zn(II), Cd(II) and As(V) by natural, acid activated and calcinated halloysite. Geol Geophys Environ [Internet]. 2015 Aug 5;41(1):108–9. Available from: .
13. 13. Deng L, Yuan P, Liu D, Annabi-Bergaya F, Zhou J, Chen F, et al. Effects of microstructure of clay minerals, montmorillonite, kaolinite and halloysite, on their benzene adsorption behaviors. Appl Clay Sci [Internet]. 2017 Jul 1;143:184–91. Available from: .
14. 14. Kiani G, Soltanzadeh M, Ahadzadeh I. Adsorption study of Zinc ion onto halloysite nanotubes using taguchi’s design of experimental methodology. Int J Nano Dimens [Internet]. 2018 Aug 1;9(3):246–59. Available from: .
15. 15. Tian X, Wang W, Tian N, Zhou C, Yang C, Komarneni S. Cr(VI) reduction and immobilization by novel carbonaceous modified magnetic Fe3O4/halloysite nanohybrid. J Hazard Mater [Internet]. 2016 May 15;309:151–6. Available from: .
16. 16. Silva SM, Peixoto AF, Freire C. HSO3-functionalized halloysite nanotubes: New acid catalysts for esterification of free fatty acid mixture as hybrid feedstock model for biodiesel production. Appl Catal A Gen [Internet]. 2018 Nov 25;568:221–30. Available from: .
17. 17. Leng Y. Materials Characterization: Introduction to Microscopic and Spectroscopic Methods. Singapore: John wiley & Sons (Asia) Pte Ltd; 2008.
18. 18. Peixoto AF, Fernandes AC, Pereira C, Pires J, Freire C. Physicochemical characterization of organosilylated halloysite clay nanotubes. Microporous Mesoporous Mater [Internet]. 2016 Jan 1;219:145–54. Available from: .
19. 19. Gaaz T, Sulong A, Kadhum A, Nassir M, Al-Amiery A. Impact of Sulfuric Acid Treatment of Halloysite on Physico-Chemic Property Modification. Materials (Basel) [Internet]. 2016 Jul 26;9(8):620. Available from: .
20. 20. Peña L, Hohn KL, Li J, Sun XS, Wang D. Synthesis of Propyl-Sulfonic Acid-Functionalized Nanoparticles as Catalysts for Cellobiose Hydrolysis. J Biomater Nanobiotechnol [Internet]. 2014 Sep 30;5(4):241–53. Available from: .
21. 21. Wang P, Tang Y, Liu Y, Wang T, Wu P, Lu X-Y. Halloysite nanotube@carbon with rich carboxyl groups as a multifunctional adsorbent for the efficient removal of cationic Pb(II), anionic Cr(VI) and methylene blue (MB). Environ Sci Nano [Internet]. 2018 Oct 11;5(10):2257–68. Available from: .
22. 22. Gaaz T, Sulong A, Kadhum A, Nassir M, Al-Amiery A. Surface Improvement of Halloysite Nanotubes. Appl Sci [Internet]. 2017 Mar 16;7(3):291. Available from: .
23. 23. Feng J, Fan H, Zha D, Wang L, Jin Z. Characterizations of the Formation of Polydopamine-Coated Halloysite Nanotubes in Various pH Environments. Langmuir [Internet]. 2016 Oct 11;32(40):10377–86. Available from: .
24. 24. Liu J, Wang C, Cui J, Li J, Li Q, Liu M, et al. Mesoporous carbon prepared by etching halloysite nanotubes (HNTs) with pyrrole as a precursor for a sulfur carrier of superior lithium–sulfur batteries. RSC Adv [Internet]. 2019 Apr 23;9(22):12331–8. Available from: .
25. 25. Wang A, Kang F, Huang Z, Guo Z, Chuan X. Synthesis of mesoporous carbon nanosheets using tubular halloysite and furfuryl alcohol by a template-like method. Microporous Mesoporous Mater [Internet]. 2008 Feb 1;108(1–3):318–24. Available from: .
26. 26. Amarasinghe BMWPK, Williams RA. Tea waste as a low cost adsorbent for the removal of Cu and Pb from wastewater. Chem Eng J [Internet]. 2007 Aug 1;132(1–3):299–309. Available from: .
27. 27. Zendelska A, Golomeova M. Effect of competing cations (Cu, Zn, Mn, Pb) adsorbed by natural zeolite. Int J Sci Eng Technol [Internet]. 2014;2(5):483–92. Available from: .