Environmental Science and Pollution Research

, Volume 26, Issue 18, pp 18098–18112 | Cite as

Removal of Cr(III) from aqueous solution by silica-gel/PAMAM dendrimer hybrid materials

  • Rutao Yin
  • Yuzhong NiuEmail author
  • Baoshui Zhang
  • Hou Chen
  • Zhenglong Yang
  • Lixia Yang
  • Yuming Cu
Research Article


Water pollution caused by Cr(III) is a serious environmental problem which bring adverse effect to environmental protection and public safety. Efficient removal of Cr(III) from aqueous solution is important for the remediation of Cr(III) pollution. Herein, a series of silica-gel/polyamidoamine (PAMAM) dendrimer hybrid materials (SG-G0~SG-G4.0) were used for the removal of Cr(III) from aqueous solution. The factors that affect the adsorption were extensively studied and the adsorption mechanism was demonstrated based on the experimental results and density functional theory (DFT) calculation. Result demonstrates the adsorption capacity of ester-terminated silica-gel/PAMAM dendrimers follow the order of SG-G2.5 > SG-G3.5 > SG-G1.5 > SG-G0.5, while that of amino-terminated ones decrease in the order of SG-G2.0 > SG-G4.0 > SG-G3.0 > SG-G1.0 > SG-G0. The highest adsorption is achieved at pH 4.0 for both ester- and amino-terminated materials. Adsorption kinetic indicates the adsorption equilibrium can be reached at about 240 and 180 min for amino- and ester-terminated hybrids, respectively. Adsorption kinetic can be well fitted by pseudo-second-order kinetic model with film diffusion process as the rate-limiting step. Adsorption isotherm follows Langmuir model with monolayer adsorption behavior. Fourier transform infrared spectra (FTIR) indicate the adsorption of Cr(III) by PAMAM dendrimer mainly involve the participation of N–H and C=O groups. DFT calculation demonstrates the uptake of Cr(III) by ester-terminated adsorbents mainly involves carbonyl oxygen and secondary amine nitrogen atoms to form tetra-coordinated chelate, while that of amino-terminated one tends to form hexa-coordinated chelates by carbonyl oxygen, primary and secondary amine nitrogen atoms.


Adsorption Silica-gel PAMAM dendrimers Cr(III) Mechanism 



The authors are grateful for the financial support by the National Natural Science Foundation of China (21307053 and 51673090), Natural Science Foundation of Shandong Province (ZR2018MB039), Science and Technology Research Program of Yantai (2017ZH060), The Key Program for Basic Research of Natural Science Foundation of Shandong Province (ZR2018ZC0946).


  1. Aguila B, Sun Q, Perman JA, Earl LD, Abney CW, Elzein R, Schlaf R, Ma S (2017) Efficient mercury capture using functionalized porous organic polymer. Adv Mater 29(31):1–6CrossRefGoogle Scholar
  2. Ali SA, Rachman IB, Saleh TA (2017) Simultaneous trapping of Cr(III) and organic dyes by a pH-responsive resin containing zwitterionic aminomethylphosphonate ligands and hydrophobic pendants. Chem Eng J 330:663–674CrossRefGoogle Scholar
  3. Awual MR, Yaita T, El-Safty SA, Shiwaku H, Suzuki S, Okamoto Y (2013) Copper(II) ions capturing from water using ligand modified a new type mesoporous adsorbent. Chem Eng J 221:322–330CrossRefGoogle Scholar
  4. Awual MR (2015) A novel facial composite adsorbent for enhanced copper(II) detection and removal from wastewater. Chem Eng J 266:368–375CrossRefGoogle Scholar
  5. Awual MR (2016) Assessing of lead(III) capturing from contaminated wastewater using ligand doped conjugate adsorbent. Chem Eng J 289:65–73CrossRefGoogle Scholar
  6. Awual MR, Hasan MM, Khaleque MA, Sheikh MC (2016a) Treatment of copper(II) containing wastewater by a newly developed ligand based facial conjugate materials. Chem Eng J 288:368–376CrossRefGoogle Scholar
  7. Awual MR, Miyazaki Y, Taguchi T, Shiwaku H, Yaita T (2016b) Encapsulation of cesium from contaminated water with highly selective facial organic–inorganic mesoporous hybrid adsorbent. Chem Eng J 291:128–137CrossRefGoogle Scholar
  8. Awual MR (2017a) New type mesoporous conjugate material for selective optical copper(II) ions monitoring & removal from polluted waters. Chem Eng J 307:85–94CrossRefGoogle Scholar
  9. Awual MR (2017b) Novel nanocomposite materials for efficient and selective mercury ions capturing from wastewater. Chem Eng J 307:456–465CrossRefGoogle Scholar
  10. Awual MR, Alharthi NH, Hasan MM, Karim MR, Islam A, Znad H, Hossain MA, Halim ME, Rahman MM, Khaleque MA (2017) Inorganic-organic based novel nano-conjugate material for effective cobalt(II) ions capturing from wastewater. Chem Eng J 324:130–139CrossRefGoogle Scholar
  11. Awual MR, Khraisheh M, Alharthi NH, Luqman M, Islam A, Rezaul Karim M, Rahman MM, Khaleque MA (2018) Efficient detection and adsorption of cadmium(II) ions using innovative nano-composite materials. Chem Eng J 343:118–127CrossRefGoogle Scholar
  12. Aydin YA, Aksoy ND (2009) Adsorption of chromium on chitosan: optimization, kinetics and thermodynamics. Chem Eng J 151(1-3):188–194CrossRefGoogle Scholar
  13. Barakat MA, Ramadan MH, Alghamdi MA, Algarny SS, Woodcock HL, Kuhn JN (2013) Remediation of Cu(II), Ni(II), and Cr(III) ions from simulated wastewater by dendrimer/titania composites. J Environ Manage 117:50–57CrossRefGoogle Scholar
  14. Boyd GE, Adamson AW, Myers LS (1947) The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics1. J Am Chem Soc 69(11):2836–2848CrossRefGoogle Scholar
  15. Chen X, Lam KF, Yeung KL (2011) Selective removal of chromium from different aqueous systems using magnetic MCM-41 nanosorbents. Chem Eng J 172(2-3):728–734CrossRefGoogle Scholar
  16. Da'na E, Sayari A (2012) Adsorption of heavy metals on amine-functionalized SBA-15 prepared by co-condensation: applications to real water samples. Desalination 285:62–67CrossRefGoogle Scholar
  17. Dias D, Lapa N, Bernardo M, Ribeiro W, Matos I, Fonseca I, Pinto F (2018) Cr(III) removal from synthetic and industrial wastewaters by using co-gasification chars of rice waste streams. Bioresource Technol 266:139–150CrossRefGoogle Scholar
  18. Egodawatte S, Datt A, Burns EA, Larsen SC (2015) Chemical insight into the adsorption of chromium(III) on iron oxide/mesoporous silica nanocomposites. Langmuir 31(27):7553–7562CrossRefGoogle Scholar
  19. Peer FE, Bahramifar N, Younesi H (2018) Removal of Cd(II), Pb(II) and Cu(II) ions from aqueous solution by polyamidoamine dendrimer grafted magnetic graphene oxide nanosheets. J Taiwan Inst Chem E 87:225–240CrossRefGoogle Scholar
  20. Gans J, Wolinsky M, Dunbar J (2005) Computational improvements reveal great bacterial diversity and high metal toxicity in soil. Science 309(5739):1387–1390CrossRefGoogle Scholar
  21. Godinho D, Dias D, Bernardo M, Lapa N, Fonseca I, Lopes H, Pinto F (2017) Adding value to gasification and co-pyrolysis chars as removal agents of Cr3+. J Hazard Mater 321:173–182CrossRefGoogle Scholar
  22. Hawari A, Khraisheh M, Al-Ghouti MA (2014) Characteristics of olive mill solid residue and its application in remediation of Pb2+, Cu2+ and Ni2+ from aqueous solution: mechanistic study. Chem Eng J 251:329–336CrossRefGoogle Scholar
  23. Ho YS (2006) Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods. Water Res 40(1):119–125CrossRefGoogle Scholar
  24. Ho YS, McKay G (1998) Kinetic models for the sorption of dye from aqueous solution by wood. Process Saf Environ 76(2):183–191CrossRefGoogle Scholar
  25. Jiang Y, Gao Q, Yu H, Chen Y, Deng F (2007) Intensively competitive adsorption for heavy metal ions by PAMAM-SBA-15 and EDTA-PAMAM-SBA-15 inorganic–organic hybrid materials. Micropor Mesopor Mat 103(1-3):316–324CrossRefGoogle Scholar
  26. Kommu A, Velachi V, Natalia M, Cordeiro DS, Singh JK (2017) Removal of Pb(II) ion using PAMAM dendrimer grafted graphene and graphene oxide surfaces: a molecular dynamics study. J Phys Chem A 121(48):9320–9329CrossRefGoogle Scholar
  27. Lang HG, Maldonado S, Stevenson KJ, Chandler BD (2004) Synthesis and characterization of dendrimer templated supported bimetallic Pt-Au nanoparticles. J Am Chem Soc 126(40):12949–12956CrossRefGoogle Scholar
  28. Lin S, Reddy DHK, Bediako JK, Song MH, Wei W, Kim JA, Yun YS (2017) Effective adsorption of Pd(II), Pt(IV) and Au(III) by Zr(IV)-based metal-organic frameworks from strongly acidic solutions. J Mater Chem A 5(26):13557–13564CrossRefGoogle Scholar
  29. Liu W, Jin LD, Xu J, Liu J, Li YY, Zhou PP, Wang CC, Dahlgren RA, Wang XD (2019) Insight into pH dependent Cr(VI) removal with magnetic Fe3S4. Chem Eng J 359:564–571CrossRefGoogle Scholar
  30. Luther S, Brogfeld N, Kim J, Parsons JG (2013) Study of the thermodynamics of chromium(III) and chromium(VI) binding to iron(II/III)oxide or magnetite or ferrite and manganese(II) iron (III) oxide or jacobsite or manganese ferrite nanoparticles. J Colloid Interf Sci 400:97–103CrossRefGoogle Scholar
  31. Ma L, Wang Q, Islam SM, Liu Y, Ma S, Kanatzidis MG (2016) Highly selective and efficient removal of heavy metals by layered double hydroxide intercalated with the MoS4 2- ion. J Am Chem Soc 138(8):2858–2866CrossRefGoogle Scholar
  32. Ma L, Islam SM, Xiao C, Zhao J, Liu H, Yuan M, Sun G, Li H, Ma S, Kanatzidis MG (2017) Rapid simultaneous removal of toxic anions [HSeO3]-, [SeO3]2-, and [SeO4]2-, and metals Hg2+, Cu2+, and Cd2+ by MoS4 2- intercalated layered double hydroxide. J Am Chem Soc 139(39):12745–12757CrossRefGoogle Scholar
  33. Niu Y, Qu R, Sun C, Wang C, Chen H, Ji C, Zhang Y, Shao X, Bu F (2013) Adsorption of Pb(II) from aqueous solution by silica-gel supported hyperbranched polyamidoamine dendrimers. J Hazard Mater 244:276–286CrossRefGoogle Scholar
  34. Niu Y, Qu R, Chen H, Mu L, Liu X, Wang T, Zhang Y, Sun C (2014) Synthesis of silica gel supported salicylaldehyde modified PAMAM dendrimers for the effective removal of Hg(II) from aqueous solution. J Hazard Mater 278:267–278CrossRefGoogle Scholar
  35. Parab H, Joshi S, Shenoy N, Lali A, Sarma US, Sudersanan M (2006) Determination of kinetic and equilibrium parameters of the batch adsorption of Co(II), Cr(III) and Ni(II) onto coir pith. Process Biochem 41(3):609–615CrossRefGoogle Scholar
  36. Qu R, Niu Y, Sun C, Ji C, Wang C, Cheng G (2006) Syntheses, characterization, and adsorption properties for metal ions of silica-gel functionalized by ester- and amino-terminated dendrimer-like polyamidoamine polymer. Micropor Mesopor Mat 97(1-3):58–65CrossRefGoogle Scholar
  37. Reichenberg D (1953) Properties of ion-exchange resins in relation to their structure. III. Kinetics of exchange. J Am Chem Soc 75(3):589–597CrossRefGoogle Scholar
  38. Selim AQ, Mohamed EA, Mobarak M, Zayed AM, Seliem MK, Komarneni S (2018) Cr(VI) uptake by a composite of processed diatomite with MCM-41: isotherm, kinetic and thermodynamic studies. Micropor Mesopor Mat 260:84–92CrossRefGoogle Scholar
  39. Shahat A, Awual MR, Khaleque MA, Alam MZ, Naushad M, Chowdhury AMS (2015) Large-pore diameter nano-adsorbent and its application for rapid lead(II) detection and removal from aqueous media. Chem Eng J 273:286–295CrossRefGoogle Scholar
  40. Shi S, Yang J, Liang S, Li M, Gan Q, Xiao K, Hu J (2018a) Enhanced Cr(VI) removal from acidic solutions using biochar modified by Fe3O4@SiO2-NH2 particles. Sci Total Environ 628-629:499–508CrossRefGoogle Scholar
  41. Shi Z, Xu C, Lu P, Fan L, Liu Y, Wang Y, Liu L, Li L (2018b) Preparation and the adsorption ability of thiolated magnetic core-shell Fe3O4@SiO2@C-SH for removing Hg2+ in water solution. Mater Lett 225:130–133CrossRefGoogle Scholar
  42. Singh KK, Talat M, Hasan SH (2006) Removal of lead from aqueous solutions by agricultural waste maize bran. Bioresource Technol 97(16):2124–2130CrossRefGoogle Scholar
  43. Song X, Niu Y, Qiu Z, Zhang Z, Zhou Y, Zhao J, Chen H (2017a) Adsorption of Hg(II) and Ag(I) from fuel ethanol by silica gel supported sulfur-containing PAMAM dendrimers: kinetics, equilibrium and thermodynamics. Fuel 206:80–88CrossRefGoogle Scholar
  44. Song X, Niu Y, Zhang P, Zhang C, Zhang Z, Zhu Y, Qu R (2017b) Removal of Co(II) from fuel ethanol by silica-gel supported PAMAM dendrimers: combined experimental and theoretical study. Fuel 199:91–101CrossRefGoogle Scholar
  45. Sun P, Liu ZT, Liu ZW (2009) Chemically modified chicken feather as sorbent for removing toxic chromium(VI) ions. Ind Eng Chem Res 48(14):6882–6889CrossRefGoogle Scholar
  46. Sun Q, Yang Y, Zhao Z, Zhang Q, Zhao X, Nie G, Jiao T, Peng Q (2018) Elaborate design of polymeric nanocomposites with Mg(II)-buffering nanochannels for highly efficient and selective removal of heavy metals from water: case study for Cu(II). Environ Sci: Nano 5(10):2440–2451Google Scholar
  47. Suwalsky M, Castro R, Villena F, Sotomayor CP (2008) Cr(III) exerts stronger structural effects than Cr(VI) on the human erythrocyte membrane and molecular models. J Inorg Biochem 102(4):842–849CrossRefGoogle Scholar
  48. Takafuji M, Ide S, Ihara H, Xu ZH (2004) Preparation of poly(1-vinylimidazole)-grafted magnetic nanoparticles and their application for removal of metal ions. Chem Mater 16(10):1977–1983CrossRefGoogle Scholar
  49. Wang J, Yang Q, Yang W, Pei H, Zhang L, Zhang T, Hu N, Suo Y, Wang J (2018) Adsorptive catalysis of hierarchical porous heteroatom-doped biomass: from recovered heavy metal to efficient pollutant decontamination. J Mate Chem A 6(34):16690–16698CrossRefGoogle Scholar
  50. Wang T, Liu W, Xiong L, Xu N, Ni J (2013) 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 215-216:366–374CrossRefGoogle Scholar
  51. Witek-Krowiak A, Harikishore Kumar Reddy D (2013) Removal of microelemental Cr(III) and Cu(II) by using soybean meal waste—unusual isotherms and insights of binding mechanism. Bioresource Technol 127: 350-357Google Scholar
  52. Wu S, Li F, Xu R, Wei S, Li G (2010) Synthesis of thiol-functionalized MCM-41 mesoporous silicas and its application in Cu(II), Pb(II), Ag(I), and Cr(III) removal. J Nanopart Res 12(6):2111–2124CrossRefGoogle Scholar
  53. Xia M, Ye C, Pi K, Liu D, Gerson AR (2018) Cr(III) removal from simulated solution using hydrous magnesium oxide coated fly ash: optimization by response surface methodology (RSM). Chinese J Chem Eng 26(5):1192–1199CrossRefGoogle Scholar
  54. Yang ZH, Xiong S, Wang B, Li Q, Yang WC (2013) Cr(III) adsorption by sugarcane pulp residue and biochar. J Cent South Univ 20(5):1319–1325CrossRefGoogle Scholar
  55. Zhang Q, Yang Q, Phanlavong P, Li Y, Wang Z, Jiao T, Peng Q (2017) Highly efficient lead(II) sequestration using size-controllable polydopamine microspheres with superior application capability and rapid capture. ACS Sustain Chem Eng 5(5):4161–4170CrossRefGoogle Scholar
  56. Zhang Q, Bolisetty S, Cao Y, Handschin S, Adamcik J, Peng Q, Mezzenga R (2019a) Selective and efficient removal of fluoride from water: in situ engineered amyloid fibril/ZrO2 hybrid membranes. Angew Chem Inter Edit Doi.
  57. Zhang Z, Niu Y, Chen H, Yang Z, Bai L, Xue Z, Yang H (2019b) Feasible one-pot sequential synthesis of aminopyridine functionalized magnetic Fe3O4 hybrids for robust capture of aqueous Hg(II) and Ag(I). ACS Sustainable Chem Eng 7:7324–7337CrossRefGoogle Scholar
  58. Zhao J, Niu Y, Ren B, Chen H, Zhang S, Jin J, Zhang Y (2018) Synthesis of Schiff base functionalized superparamagnetic Fe3O4 composites for effective removal of Pb(II) and Cd(II) from aqueous solution. Chem Eng J 347:574–584CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemistry and Materials ScienceLudong UniversityYantaiChina

Personalised recommendations