Carbon Letters

, Volume 29, Issue 1, pp 1–20 | Cite as

Preparation and characterization of functionalized MWCNTs-COOH with 3-amino-5-phenylpyrazole as an adsorbent and optimization study using central composite design

  • Mobina Alimohammady
  • Mansour JahangiriEmail author
  • Farhoush Kiani
  • Hasan Tahermansouri
Original Article


Carboxylated multi-wall carbon nanotubes (MWCNTs-COOH) was functionalized with 3-amino-5-phenylpyrazole (MWCNTs-f) and characterized by FTIR, EDX, SEM, XRD and TGA. The MWCNTs-COOH and MWCNTs-f were used for the adsorption of Cd(II), Hg(II), and As(III) ions from aqueous solutions. Additionally, to study the influence of pH, adsorbent dose, and initial ions concentration on the adsorption process, the central composite design (CCD) was applied. The quadratic model was used for analysis of variance and indicated that adsorption of metal ions strongly depends on pH. Time-dependent adsorption can be described by the pseudo-second-order kinetic model, and adsorption process was modeled by Langmuir isotherm for the adsorbents. Thermodynamic analysis showed that the adsorption of Cd(II), Hg(II) and As(III) ions were spontaneous and endothermic. Moreover, the competitive adsorption capacities of the heavy metal ions were slightly lower than noncompetitive ones. The same affinity order was observed under noncompetitive and competitive adsorption: As(III) > Cd(II) > Hg(II) in the case of MWCNTs-f. Desorption study revealed the favorable regeneration ability of adsorbents powders, even after three adsorption–desorption cycles.


Adsorption Heavy metal Carbon nanotubes 3-Amino-5-phenylpyrazole 



The financial and encouragement support provided by the Research Vice Presidency of Semnan University and Research Laboratory of Department of Chemistry, Faculty of Science, Ayatollah Amoli Branch, IAU.


  1. 1.
    Veličković ZS, Bajić ZJ, Ristić MĐ, Djokić VR, Marinković AD, Uskoković PS, Vuruna MM (2013) Modification of multi-wall carbon nanotubes for the removal of cadmium, lead and arsenic from wastewater. Dig J Nanomater Biostruct 8Google Scholar
  2. 2.
    Alimohammady M, Ghaemi M, Saghatoleslami N (2011) A new approach for the removal of toxic pollutants and gold recovery from industrial waste water. In: 5th National seminar of chemistry and environment. 2011Google Scholar
  3. 3.
    Alimohammady M, Saghatoleslami N, Ghaemi M (2012) A simple and cost effective method for recovering gold from the jewelers’ electroplating waste water workshops using nano-wires structure of manganese oxide as an adsorbent. In: 4th international conference on nanoscience and nanotechnology. 2012Google Scholar
  4. 4.
    Sharma SK (2014) Heavy metals in water: presence, removal and safety. Royal Society of Chemistry, UKCrossRefGoogle Scholar
  5. 5.
    Huang Y, Jin B, Zhong Z, Zhong W, Xiao R (2008) Characteristic and mercury adsorption of activated carbon produced by CO2 of chicken waste. J Environ Sci 20:291CrossRefGoogle Scholar
  6. 6.
    Anirudhan TS, Sreekumari SS (2011) Adsorptive removal of heavy metal ions from industrial effluents using activated carbon derived from waste coconut buttons. J Environ Sci 23:1989CrossRefGoogle Scholar
  7. 7.
    Chen W, Parette R, Zou J, Cannon FS, Dempsey BA (2007) Arsenic removal by iron-modified activated carbon. Water Res 41:1851CrossRefGoogle Scholar
  8. 8.
    Zhang Y, Zhao L, Guo R, Song N, Wang J, Cao Y, Orndorff W, Pan WP (2015) Mercury adsorption characteristics of HBr-modified fly ash in an entrained-flow reactor. J Environ Sci 33:156CrossRefGoogle Scholar
  9. 9.
    Xu W, Wang H, Zhu T, Kuang J, Jing P (2013) Mercury removal from coal combustion flue gas by modified fly ash. J Environ Sci 25:393CrossRefGoogle Scholar
  10. 10.
    Goswami D, Das AK (2000) Removal of arsenic from drinking water using modified fly-ash bed. Int J Water 1:61CrossRefGoogle Scholar
  11. 11.
    Zamzow M, Eichbaum B, Sandgren K, Shanks D (1990) Removal of heavy metals and other cations from wastewater using zeolites. Sep Sci Technol 25:1555CrossRefGoogle Scholar
  12. 12.
    Li Z, Beachner R, McManama Z, Hanlie H (2007) Sorption of arsenic by surfactant-modified zeolite and kaolinite. Microporous Mesoporous Mater 105:291CrossRefGoogle Scholar
  13. 13.
    Peña-Rodríguez S, Bermúdez-Couso A, Nóvoa-Muñoz JC, Arias-Estévez M, Fernández-Sanjurjo MJ, Álvarez-Rodríguez E, Núñez-Delgado A (2013) Mercury removal using ground and calcined mussel shell. J Environ Sci 25:2476CrossRefGoogle Scholar
  14. 14.
    Yavuz H, Denizli A, Güngüneş H, Safarikova M, Safarik I (2006) Biosorption of mercury on magnetically modified yeast cells. Sep Purif Technol 52:253CrossRefGoogle Scholar
  15. 15.
    Rezaee A, Derayat J, Mortazavi S, Yamini Y, Jafarzadeh M (2005) Removal of mercury from chlor-alkali industry wastewater using Acetobacter xylinum cellulose. Am J Environ Sci 1:102CrossRefGoogle Scholar
  16. 16.
    Al Rmalli SW, Harrington CF, Ayub M, Haris PI (2005) A biomaterial based approach for arsenic removal from water. J Environ Monit 7:279CrossRefGoogle Scholar
  17. 17.
    Thirumavalavan M, Lai Y-L, Lin L-C, Lee J-F (2009) Cellulose-based native and surface modified fruit peels for the adsorption of heavy metal ions from aqueous solution: Langmuir adsorption isotherms. J Chem Eng Data 55:1186CrossRefGoogle Scholar
  18. 18.
    Gupta RK, Singh RA, Dubey SS (2004) Removal of mercury ions from aqueous solutions by composite of polyaniline with polystyrene. Sep Purif Technol 38:225CrossRefGoogle Scholar
  19. 19.
    Bessbousse H, Rhlalou T, Verchère JF, Lebrun L (2010) Mercury removal from wastewater using a poly(vinylalcohol)/poly(vinylimidazole) complexing membrane. Chem Eng J 164:37CrossRefGoogle Scholar
  20. 20.
    Vatutsina OM, Soldatov VS, Sokolova VI, Johann J, Bissen M, Weissenbacher A (2007) A new hybrid (polymer/inorganic) fibrous sorbent for arsenic removal from drinking water. React Funct Polym 67:184CrossRefGoogle Scholar
  21. 21.
    Sumesh E, Bootharaju M, Pradeep T (2011) A practical silver nanoparticle-based adsorbent for the removal of Hg2+ from water. J Hazard Mater 189:450CrossRefGoogle Scholar
  22. 22.
    Ojea-Jiménez I, López XN, Arbiol J, Puntes V (2012) Citrate-coated gold nanoparticles as smart scavengers for mercury (II) removal from polluted waters. ACS nano 6:2253CrossRefGoogle Scholar
  23. 23.
    Yu L, Peng X, Ni F, Li J, Wang D, Luan Z (2013) Arsenite removal from aqueous solutions by γ-Fe2O3–TiO2 magnetic nanoparticles through simultaneous photocatalytic oxidation and adsorption. J Hazard Mater 246:10CrossRefGoogle Scholar
  24. 24.
    Shi J, Li H, Lu H, Zhao X (2015) Use of carboxyl functional magnetite nanoparticles as potential sorbents for the removal of heavy metal ions from aqueous solution. J Chem Eng Data 60:2035CrossRefGoogle Scholar
  25. 25.
    Yang Y, Liang L, Wang D (2008) Effect of dissolved organic matter on adsorption and desorption of mercury by soils. J Environ Sci 20:1097CrossRefGoogle Scholar
  26. 26.
    Manning BA, Goldberg S (1997) Arsenic (III) and arsenic (V) adsorption on three california soilS. Soil Sci 162:886CrossRefGoogle Scholar
  27. 27.
    Sonmez HB, Senkal B, Sherrington D, Bıcak N (2003) Atom transfer radical graft polymerization of acrylamide from N-chlorosulfonamidated polystyrene resin, and use of the resin in selective mercury removal. React Funct Polym 55:1CrossRefGoogle Scholar
  28. 28.
    Rivas B, Maturana H, Luna M (1999) Selective binding of mercury ions by poly (4-vinylpyridine) hydrochloride resin. J Appl Polym Sci 74:1557CrossRefGoogle Scholar
  29. 29.
    Balaji T, Yokoyama T, Matsunaga H (2005) Adsorption and removal of As (V) and As (III) using Zr-loaded lysine diacetic acid chelating resin. Chemosphere 59:1169CrossRefGoogle Scholar
  30. 30.
    Elassar A-ZA, El-Dissouky A, Jeragh B, Bu-olian AH, Rizk S (2010) Synthesis and characterization of sulfonylamberlite-xad-16-based chelating resins: complexation and application for the selective removal of some heavy metals. J Chem Eng Data 55:4830CrossRefGoogle Scholar
  31. 31.
    Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56CrossRefGoogle Scholar
  32. 32.
    Guldi DM, Martín N (2010) Carbon nanotubes and related structures: synthesis, characterization, functionalization, and applications. Wiley, USA, p 103CrossRefGoogle Scholar
  33. 33.
    Amiri A, Shanbedi M, Savari M, Chew B, Kazi S ((2015)) Cadmium ion sorption from aqueous solutions by high surface area ethylenediaminetetraacetic acid and diethylene triamine pentaacetic acid-treated carbon nanotubes. RSC Adv 5Google Scholar
  34. 34.
    Rao GP, Lu C, Su F (2007) Sorption of divalent metal ions from aqueous solution by carbon nanotubes: a review. Sep Purif Technol 58:224CrossRefGoogle Scholar
  35. 35.
    Yang K, Wu W, Jing Q, Zhu L (2008) Aqueous adsorption of aniline, phenol, and their substitutes by multi-walled carbon nanotubes. Environ Sci Technol 42:7931CrossRefGoogle Scholar
  36. 36.
    Gao Z, Bandosz TJ, Zhao Z, Han M, Qiu J (2009) Investigation of factors affecting adsorption of transition metals on oxidized carbon nanotubes. J Hazard Mater 167:357CrossRefGoogle Scholar
  37. 37.
    Xu D, Tan X, Chen C, Wang X (2008) Removal of Pb(II) from aqueous solution by oxidized multiwalled carbon nanotubes. J Hazard Mater 154:407CrossRefGoogle Scholar
  38. 38.
    Tahermansouri H, Ahi RM, Kiani F (2014) Kinetic, equilibrium and isotherm studies of cadmium removal from aqueous solutions by oxidized multi-walled carbon nanotubes and the functionalized ones with thiosemicarbazide and their toxicity investigations: a comparison. J Chin Chem Soc 61:1188CrossRefGoogle Scholar
  39. 39.
    Alimohammady M, Jahangiri M, Kiani F, Tahermansouri H (2017) A new modified MWCNTs with 3-aminopyrazole as a nanoadsorbent for Cd (II) removal from aqueous solutions. J Environ Chem Eng 5:3405CrossRefGoogle Scholar
  40. 40.
    Alimohammady M, Jahangiri M, Kiani F, Tahermansouri H (2017) Highly efficient simultaneous adsorption of Cd (ii), Hg (ii) and As (iii) ions from aqueous solutions by modification of graphene oxide with 3-aminopyrazole: central composite design optimization. New J Chem 41:8905CrossRefGoogle Scholar
  41. 41.
    Alimohammady M, Jahangiri M, Kiani F, Tahermansouri H (2018) Design and evaluation of functionalized multi-walled carbon nanotubes by 3-aminopyrazole for the removal of Hg(II) and As (III) ions from aqueous solution. Res Chem Intermed 44:69CrossRefGoogle Scholar
  42. 42.
    Lenth RV (2009) Response-surface methods in R, using rsm. J Stat Softw 32:1CrossRefGoogle Scholar
  43. 43.
    Yazdani M, Bahrami H, Arami M (2014) Preparation and characterization of chitosan/feldspar biohybrid as an adsorbent: optimization of adsorption process via response surface modeling. Sci World JGoogle Scholar
  44. 44.
    Breyfogle FW (1992) Statistical methods for testing, development, and manufacturing. Wiley, USAGoogle Scholar
  45. 45.
    Ghaedi M, Hajati S, Zare M, Jaberi SS (2015) Experimental design for simultaneous analysis of malachite green and methylene blue; derivative spectrophotometry and principal component-artificial neural network. RSC Adv 5:38939CrossRefGoogle Scholar
  46. 46.
    Shahbazi A, Younesi H, Badiei A (2013) Batch and fixed-bed column adsorption of Cu (II), Pb(II) and Cd (II) from aqueous solution onto functionalised SBA-15 mesoporous silica. Can J Chem Eng 91:739CrossRefGoogle Scholar
  47. 47.
    Vuković GD, Marinković AD, Čolić M, Ristić MĐ, Aleksić R, Perić-Grujić AA, Uskoković PS (2010) Removal of cadmium from aqueous solutions by oxidized and ethylenediamine-functionalized multi-walled carbon nanotubes. Chem Eng J 157:238CrossRefGoogle Scholar
  48. 48.
    Wang TL, Tseng CG (2007) Polymeric carbon nanocomposites from multiwalled carbon nanotubes functionalized with segmented polyurethane. J Appl Polym Sci 105:1642CrossRefGoogle Scholar
  49. 49.
    Garba ZN, Rahim AA (2014) Process optimization of K2C2O4-activated carbon from Prosopis africana seed hulls using response surface methodology. J Anal Appl Pyrolysis 107:306CrossRefGoogle Scholar
  50. 50.
    Montgomery DC (2000) Design and analysis of experiments. Wiley, United StatesGoogle Scholar
  51. 51.
    Moradi O (2011) The removal of ions by functionalized carbon nanotube: equilibrium, isotherms and thermodynamic studies. Chem Biochem Eng Q 25:229Google Scholar
  52. 52.
    Salam MA, Makki MSI, Abdelaal MYA (2011) Preparation and characterization of multi-walled carbon nanotubes/chitosan nanocomposite and its application for the removal of heavy metals from aqueous solution. J Alloy Compd 509:2582CrossRefGoogle Scholar
  53. 53.
    Rocha CG, Zaia DAM, da Silva Alfaya RV, da Silva Alfaya AA (2009) Use of rice straw as biosorbent for removal of Cu (II), Zn (II), Cd (II) and Hg(II) ions in industrial effluents. J Hazard Mater 166:383CrossRefGoogle Scholar
  54. 54.
    Shadbad MJ, Mohebbi A, Soltani A (2011) Mercury (II) removal from aqueous solutions by adsorption on multi-walled carbon nanotubes. Korean J Chem Eng 28:1029CrossRefGoogle Scholar
  55. 55.
    Tawabini BS, Al-Khaldi SF, Khaled MM, Atieh MA (2011) Removal of arsenic from water by iron oxide nanoparticles impregnated on carbon nanotubes. J Environ Sci Health A 46:215CrossRefGoogle Scholar
  56. 56.
    Ozturk D, Sahan T (2015) Design and optimization of Cu (II) adsorption conditions from aqueous solutions by low-cost adsorbent pumice with response surface methodology. Pol J Environ Stud 24:2015Google Scholar
  57. 57.
    Moustafa YM, Morsi RE, Fathy M (2014) Mercury removing capacity of multiwall carbon nanotubes as detected by cold vapor atomic absorption spectroscopy: kinetic and equilibrium studies. World Acad Sci Eng Technol Int J Chem Mol Nucl Mater Metal Eng 8:724Google Scholar
  58. 58.
    Chen B, Zhu Z, Ma J, Yang M, Hong J, Hu X, Qiu Y, Chen J (2014) One-pot, solid-phase synthesis of magnetic multiwalled carbon nanotube/iron oxide composites and their application in arsenic removal. J Colloid Interface Sci 434:9CrossRefGoogle Scholar
  59. 59.
    Hadavifar M, Bahramifar N, Younesi H, Li Q (2014) Adsorption of mercury ions from synthetic and real wastewater aqueous solution by functionalized multi-walled carbon nanotube with both amino and thiolated groups. Chem Eng J 237:217CrossRefGoogle Scholar
  60. 60.
    Kuriakose S, Singh TS, Pant KK (2004) Adsorption of As (III) from aqueous solution onto iron oxide impregnated activated alumina. Water Qual Res J Can 39:258CrossRefGoogle Scholar
  61. 61.
    Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I, Solids. J Am Chem Soc 38:2221CrossRefGoogle Scholar
  62. 62.
    Davodi B, Jahangiri M (2014) Determination of optimum conditions for removal of As (III) and As (V) by polyaniline/polystyrene nanocomposite. Synth Met 194:97CrossRefGoogle Scholar
  63. 63.
    Jeppu GP, Clement TP (2012) A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects. J Contam Hydrol 129:46CrossRefGoogle Scholar
  64. 64.
    Foo K, Hameed B (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2CrossRefGoogle Scholar
  65. 65.
    Aharoni C, Ungarish M (1977) Kinetics of activated chemisorption. Part 2.—Theoretical models. J Chem Soc Faraday Trans 1 Phys Chem Condens Phases 73:456Google Scholar
  66. 66.
    Tofighy MA, Mohammadi T (2011) Adsorption of divalent heavy metal ions from water using carbon nanotube sheets. J Hazard Mater 185:140CrossRefGoogle Scholar
  67. 67.
    Shahmohammadi-Kalalagh S (2011) Isotherm and kinetic studies on adsorption of Pb, Zn and Cu by kaolinite. Casp J Environ Sci 9:243Google Scholar
  68. 68.
    Azizian S (2004) Kinetic models of sorption: a theoretical analysis. J Colloid Interface Sci 276:47CrossRefGoogle Scholar
  69. 69.
    Zare-Dorabei R, Ferdowsi SM, Barzin A, Tadjarodi A (2016) Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2′-dipyridylamine: central composite design optimization. Ultrason Sonochem 32:265CrossRefGoogle Scholar
  70. 70.
    Sparks DL (2013) Kinetics of soil chemical processes. Academic Press, LondonGoogle Scholar
  71. 71.
    Abdullah AM, Mohammed AA-S, Suleyman AAM, Md Zahangir A, Iis S (2014) Kinetics of cadmium adsorption by CNTs grown on PACs. Int J Nanoelectron Mater 7:25Google Scholar
  72. 72.
    Salam MA, Al-Zhrani G, Kosa SA (2012) Simultaneous removal of copper(II), lead(II), zinc(II) and cadmium(II) from aqueous solutions by multi-walled carbon nanotubes. C R Chim 15:398CrossRefGoogle Scholar
  73. 73.
    Tawabini B, Al-Khaldi S, Atieh M, Khaled M (2010) Removal of mercury from water by multi-walled carbon nanotubes. Water Sci Technol 61:591CrossRefGoogle Scholar
  74. 74.
    Karadag D, Turan M, Akgul E, Tok S, Faki A (2007) Adsorption equilibrium and kinetics of reactive black 5 and reactive red 239 in aqueous solution onto surfactant-modified zeolite. J Chem Eng Data 52:1615CrossRefGoogle Scholar
  75. 75.
    Moghaddam HK, Pakizeh M (2015) Experimental study on mercury ions removal from aqueous solution by MnO 2/CNTs nanocomposite adsorbent. J Ind Eng Chem 21:221CrossRefGoogle Scholar
  76. 76.
    Li Y-H, Ding J, Luan Z, Di Z, Zhu Y, Xu C, Wu D, Wei B (2003) Competitive adsorption of Pb2 + , Cu2 + and Cd2 + ions from aqueous solutions by multiwalled carbon nanotubes. Carbon 41:2787CrossRefGoogle Scholar
  77. 77.
    Kosa SA, Al-Zhrani G, Salam MA (2012) Removal of heavy metals from aqueous solutions by multi-walled carbon nanotubes modified with 8-hydroxyquinoline. Chem Eng J 181:159CrossRefGoogle Scholar
  78. 78.
    Say R, Yılmaz N, Denizli A (2003) Biosorption of cadmium, lead, mercury, and arsenic ions by the fungus Penicillium purpurogenum. Sep Sci Technol 38:2039CrossRefGoogle Scholar
  79. 79.
    Denizli A, Say R, Testereci HN, Arica MY (1999) Procion blue MX-3G-attached microporous poly (2-hydroxyethyl methacrylate) membranes for copper, arsenic, cadmium, and mercury adsorption. Sep Sci Technol 34:2369CrossRefGoogle Scholar
  80. 80.
    Akl MA, Abou-Elanwar AM (2015) Adsorption studies of Cd (II) from water by acid modified multiwalled carbon nanotubes. J Nanomed Nanotechnol 6:1Google Scholar
  81. 81.
    Ma J, Zhu Z, Chen B, Yang M, Zhou H, Li C, Yu F, Chen J (2013) One-pot, large-scale synthesis of magnetic activated carbon nanotubes and their applications for arsenic removal. J Mater Chem A 1:4662CrossRefGoogle Scholar
  82. 82.
    Ntim SA, Mitra S (2012) Adsorption of arsenic on multiwall carbon nanotube–zirconia nanohybrid for potential drinking water purification. J Colloid Interface Sci 375:154CrossRefGoogle Scholar

Copyright information

© Korean Carbon Society 2019

Authors and Affiliations

  • Mobina Alimohammady
    • 1
  • Mansour Jahangiri
    • 1
    Email author
  • Farhoush Kiani
    • 2
  • Hasan Tahermansouri
    • 2
  1. 1.Faculty of Chemical, Petroleum and Gas EngineeringSemnan UniversitySemnanIslamic Republic of Iran
  2. 2.Department of Chemistry, Ayatollah Amoli BranchIslamic Azad UniversityAmolIslamic Republic of Iran

Personalised recommendations