Skip to main content
Log in

Solid phase extractors derived by functionalising sub-micro silica gel with chelating agents and their pH-tunable adsorbing capability towards Pb(II) and Ag(I)

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

Three novel solid phase extraction agents were developed by functionalising sub-micron sized silica gel with organic functional moieties possessing {SN}-ligating atoms. The extractors were characterised by FTIR and TGA. Their capability of adsorbing the ions Fe(III), Cu(II), Zn(II), Cd(II), Cr(VI), Hg(II), Pb(II), Co(II), Ni(II), and Ag(I) is described. The extractors show pH-tunable selectivity for Ag(I) and/or Pb(II). By adjusting the pH to 5 or 6, high affinity is found for both Ag(I) and Pb(II), with little or no interference by the other metal ions. At pH values of <2, the extractors become highly selective for Ag(I), with an adsorption capacity of 35 mg g−1. Little mechanical stirring is required due to the size of the particles. The recovery rates for both Ag(I) and Pb(II) were better 90% even after five repetitive adsorption-desorption cycles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Wang XX, Wang S, Yang WS, Shan Z (2009) Ultrasonic synthesis of Fe3O4@SiO2 nano-composite magnetic particles for plasmid DNA purification. Acta Chim Sinica 67:54–58

    CAS  Google Scholar 

  2. Arguello J, Leidens VL, Magosso HA, Ramos RR, Gushikem Y (2008) Simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid by methylene blue adsorbed on a phosphorylated zirconia-silica composite electrode. Electrochim Acta 54:560–565

    Article  CAS  Google Scholar 

  3. Boddi K, Takatsy A, Szabo S, Marko L, Mark L, Wittmann I, Ohmacht R, Montsko G, Vallant RM, Ringer T, Bakry R, Huck CW, Bonn GK, Szabo Z (2009) Use of fullerene-, octadecyl-, and triaconthyl silica for solid phase extraction of tryptic peptides obtained from unmodified and in vitro glycated human serum albumin and fibrinogen. J Sep Sci 32:295–308

    Article  CAS  Google Scholar 

  4. Huang SS, Fan Y, Cheng ZY, Kong DY, Yang PP, Quan ZW, Zhang CM, Lin J (2009) Magnetic mesoporous silica spheres for drug targeting and controlled release. J Phys Chem C 113:1775–1784

    Article  CAS  Google Scholar 

  5. Klichko Y, Liong M, Choi E, Angelos S, Nel AE, Stoddart JF, Tamanoi F, Zink JI (2009) Mesostructured silica for optical functionality, nanomachines, and drug delivery. J Am Ceram Soc 92:S2–S10

    Article  CAS  Google Scholar 

  6. Xu WJ, Gao Q, Xu Y, Wu D, Sun YH (2009) pH-Controlled drug release from mesoporous silica tablets coated with hydroxypropyl methylcellulose phthalate. Mater Res Bull 44:606–612

    Article  CAS  Google Scholar 

  7. Hercules DM, Cox LE, Onisick S, Nichols GD, Carver JC (1973) Electron spectroscopy (ESCA). Use for trace analysis. Anal Chem 45:1973–1975

    Article  CAS  Google Scholar 

  8. Sugawara KF, Weetall HH, Schucker GD (1974) Preparation, properties, and applications of 8-hydroxyquinoline immobilized chelate. Anal Chem 46:489–492

    Article  CAS  Google Scholar 

  9. Leyden DE, Luttrell GH (1975) Preconcentration of trace metals using chelating groups immobilized via silylation. Anal Chem 47:1612–1617

    Article  CAS  Google Scholar 

  10. Leyden DE, Luttrell GH, Nonidez WK, Werho DB (1976) Preconcentration of certain anions using reagents immobilized via silylation. Anal Chem 48:67–70

    Article  CAS  Google Scholar 

  11. Leyden DE, Steele ML, Jablonski BB, Somoano RB (1978) Structural studies of immobilized ethylenediamine as a preconcentrating agent for molybdate and tungstate. Anal Chim Acta 100:545–554

    Article  CAS  Google Scholar 

  12. Li BZ, Chen YL, Zhao HY, Pei XF, Bi LF, Hanabusa K, Yang YG (2008) From branched self-assemblies to branched mesoporous silica nanoribbons. Chem Commun 6366–6368

  13. Etienne M, Goubert-Renaudin S, Rousselin Y, Marichal C, Denat F, Lebeau B, Walcarius A (2009) Multiarm cyclam-grafted mesoporous silica: a strategy to improve the chemical stability of silica materials functionalized with amine ligands. Langmuir 25:3137–3145

    Article  CAS  Google Scholar 

  14. Spivakov BY, Malofeeva GI, Petrukhin OM (2006) Solid-phase extraction on alkyl-bonded silica gels in inorganic analysis. Anal Sci 22:503–519

    Article  CAS  Google Scholar 

  15. Shang XH, Yan XP (2007) Selective detection of trace lead in lead-free solder alloy by flow injection on-line solid-phase extraction using a macrocycle immobilized silica gel as sorbent coupled with hydride generation atomic fluorescence spectrometry. J Anal At Spectrom 22:1284–1289

    Article  CAS  Google Scholar 

  16. Roldan PS, Alcântara IL, Padilha CCF, Padilha PM (2005) Determination of copper, iron, nickel and zinc in gasoline by FAAS after sorption and preconcentration on silica modified with 2-aminotiazole groups. Fuel 84:305–309

    Article  CAS  Google Scholar 

  17. Arenas LT, Lima EC, dos Santos JAA, Vaghetti JCP, Costa TMH, Benvenutti EV (2007) Use of statistical design of experiments to evaluate the sorption capacity of 1, 4-diazoniabicycle[2.2.2]octane/silica chloride for Cr(VI) adsorption. Colloids Surf A 297:240–248

    Article  CAS  Google Scholar 

  18. Grigoropoulou G, Stathi P, Karakassides MA, Louloudi M, Deligiannakis Y (2008) Functionalized SiO2 with N-, S-containing ligands for Pb(II) and Cd(II) adsorption. Colloids Surf A 320:25–35

    Article  CAS  Google Scholar 

  19. Blitz IP, Blitz JP, Gun’ko VM, Sheeran DJ (2007) Functionalized silicas: structural characteristics and adsorption of Cu(II) and Pb(II). Colloids Surf A 307:83–92

    Article  CAS  Google Scholar 

  20. Dogan CE, Akcin G (2007) Solid phase extraction and determination of lead in water samples using silica gel homogeneously modified by thiosalicylic acid. Anal Lett 40:2524–2543

    Article  CAS  Google Scholar 

  21. An FQ, Feng XQ, Gao BJ (2009) Adsorption mechanism and property of a novel adsorption material PAM/SiO2 towards 2, 4, 6-trinitrotoluene. J Hazard Mater 168:352–357

    Article  CAS  Google Scholar 

  22. Cabuk A, Akar T, Tunali S, Tabak O (2006) Biosorption characteristics of Bacillus sp ATS-2 immobilized in silica gel for removal of Pb(II). J Hazard Mater 136:317–323

    Article  CAS  Google Scholar 

  23. Fan J, Wu CL, Wei W, Peng CY, Peng PG (2007) Preparation of xylenol orange functionalized silica gel as a selective solid phase extractor and its application for preconcentration-separation of mercury from waters. J Hazard Mater 145:323–330

    Article  CAS  Google Scholar 

  24. Cui Y, Chang X, Zhu X, Luo H, Hu Z, Zou X, He Q (2007) Chemically modified silica gel with p-dimethylaminobenzaldehyde for selective solid-phase extraction and preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) by ICP-OES. Microchem J 87:20–26

    Article  CAS  Google Scholar 

  25. Hatay I, Gup R, Ersoz M (2008) Silica gel functionalized with 4-phenylacetophynone 4-aminobenzoylhydrazone: Synthesis of a new chelating matrix and its application as metal ion collector. J Hazard Mater 150:546–553

    Article  CAS  Google Scholar 

  26. Huang XP, Chang XJ, He Q, Cui YM, Zhai YH, Jiang N (2008) Tris(2-aminoethyl) amine functionalized silica gel for solid-phase extraction and preconcentration of Cr(III), Cd(II) and Pb(II) from waters. J Hazard Mater 157:154–160

    Article  CAS  Google Scholar 

  27. Mahmoud ME (1997) Silica gel-immobilized Eriochrome black-T as a potential solid phase extractor for zinc (II) and magnesium (II) from calcium (II). Talanta 45:309–315

    Article  CAS  Google Scholar 

  28. Perez-Quintanilla D, del Hierro I, Fajardo M, Sierra I (2006) 2-mercaptothiazoline modified mesoporous silica for mercury removal from aqueous media. J Hazard Mater 134:245–256

    Article  CAS  Google Scholar 

  29. Yin P, Xu Q, Qu RJ, Zhao GF (2009) Removal of transition metal ions from aqueous solutions by adsorption onto a novel silica gel matrix composite adsorbent. J Hazard Mater 169:228–232

    Article  CAS  Google Scholar 

  30. Ngeontae W, Aeungmaitrepirom W, Tuntulani T, Imyim A (2009) Highly selective preconcentration of Cu(II) from seawater and water samples using amidoamidoxime silica. Talanta 78:1004–1010

    Article  CAS  Google Scholar 

  31. Silva MF, Cerutti ES, Martinez LD (2006) Coupling cloud point extraction to instrumental detection systems for metal analysis. Microchim Acta 155:349–364

    Article  CAS  Google Scholar 

  32. Li MKY, Lei NY, Gong CB, Yu YJ, Lam KH, Lam MHW, Yu HX, Lam PKS (2009) An organically modified silicate molecularly imprinted solid-phase microextraction device for the determination of polybrominated diphenyl ethers. Anal Chim Acta 633:197–203

    Article  CAS  Google Scholar 

  33. Zhu XS, Wu M, Gu Y (2009) beta-Cyclodextrin-cross-linked polymer as solid phase extraction material coupled with inductively coupled plasma mass spectrometry for the analysis of trace Co(II). Talanta 78:565–569

    Article  CAS  Google Scholar 

  34. Xie FZ, Lin XC, Wu XP, Xie ZH (2008) Solid phase extraction of lead (II), copper (II), cadmium (II) and nickel (II) using gallic acid-modified silica gel prior to determination by flame atomic absorption spectrometry. Talanta 74:836–843

    Article  CAS  Google Scholar 

  35. Howard AG, Khdary NH (2005) Nanoscavenger based dispersion preconcentration; sub-micron particulate extractants for analyte collection and enrichment. Analyst 130:1432–1438

    Article  CAS  Google Scholar 

  36. Cui YM, Chang XJ, Zhai YH, Zhu XB, Zheng H, Lian N (2006) ICP-AES determination of trace elements after preconcentrated with p-dimethylaminobenzaldehyde-modified nanometer SiO2 from sample solution. Microchem J 83:35–41

    Article  CAS  Google Scholar 

  37. Cui YM, Chang XJ, Zhu XB, Jiang N, Hu Z, Lian N (2007) Nanometer SiO2 modified with 5-sulfosalicylic acid as selective solid-phase extractant for Fe(III) determination by ICP-AES from biological and natural water samples. Microchem J 86:23–28

    Article  CAS  Google Scholar 

  38. He Q, Chang XJ, Huang XP, Hu Z (2008) Determination of trace elements in food samples by ICP-AES after preconcentration with p-toluenesulfonylamide immobilized on silica gel and nanometer SiO2. Microchim Acta 160:147–152

    Article  CAS  Google Scholar 

  39. Kaur A, Gupta U (2008) Chemically Modified Submicron Silica Particulate Extractants for Preconcentration of Mercury(II). Bull Korean Chem Soc 29:1932–1936

    Article  CAS  Google Scholar 

  40. Zhai YH, Chang XJ, Cui YM, Lian N, Lai SJ, Zhen H, He Q (2006) Selective determination of trace mercury (II) after preconcentration with 4-(2-pyridylazo)-resorcinol-modified nanometer-sized SiO2 particles from sample solutions. Microchim Acta 154:253–259

    Article  CAS  Google Scholar 

  41. Zhu XB, Yang D, Chang X, Cui YM, Hu Z, Zou X (2008) Selective solid-phase extraction of trace Fe(III) from biological and natural water samples using nanometer SiO2 modified with acetylsalicylic acid. Microchim Acta 161:115–122

    Article  CAS  Google Scholar 

  42. Zhang L, Chang XJ, Hu Z, Zhang LJ, Shi JP, Gao R (2010) Selective solid phase extraction and preconcentration of mercury(II) from environmental and biological samples using nanometer silica functionalized by 2, 6-pyridine dicarboxylic acid. Microchim Acta 168:79–85

    Article  CAS  Google Scholar 

  43. Zhang M, Yuan DX, Chen GH, Li QL, Zhang Z, Liang Y (2009) Simultaneous determination of nitrite and nitrate at nanomolar level in seawater using on-line solid phase extraction hyphenated with liquid waveguide capillary cell for spectrophotometric detection. Microchim Acta 165:427–435

    Article  CAS  Google Scholar 

  44. Shariati S, Yamini Y, Faraji M, Saleh A (2009) On-line solid phase extraction coupled to ICP-OES for simultaneous preconcentration and determination of some transition elements. Microchim Acta 165:65–72

    Article  CAS  Google Scholar 

  45. Mikula B, Puzio B, Feist B (2009) Application of 1, 10-phenanthroline for preconcentration of selected heavy metals on silica gel. Microchim Acta 166:337–341

    Article  CAS  Google Scholar 

  46. Junping W, Mingfei P, Guozhen F, Shuo W (2009) Preparation of a novel molecularly imprinted polymer by a sol-gel process for on-line solid-phase extraction coupled with high performance liquid chromatography to detect trace enrofloxacin in fish and chicken samples. Microchim Acta 166:295–302

    Article  CAS  Google Scholar 

  47. Tokalioglu S, Yilmaz V, Kartal S, Delibas A, Soykan C (2009) Solid phase extraction of Pd(II) on a newly synthesized chelating resin prior to determination by flame atomic absorption spectrometry. Microchim Acta 165:347–352

    Article  CAS  Google Scholar 

  48. Papadopoulos EP, Jarrar A, Issidorides CH (1966) Oxidations with manganese dioxide. J Org Chem 31:615–616

    Article  CAS  Google Scholar 

  49. Shimojima A, Liu Z, Ohsuna T, Terasaki O, Kuroda K (2005) Self-assembly of designed oligomeric siloxanes with alkyl chains into silica-based hybrid mesostructures. J Am Chem Soc 127:14108–14116

    Article  CAS  Google Scholar 

  50. Lindoy LF, Livingstone SE (1968) Reactions of nickel chelates derived from 2-aminobenzenethiol. Inorg Chem 7:1149–1154

    Article  CAS  Google Scholar 

  51. Pesco C, Antonio de Campos E, Costa CMM (1997) Preconcentration of transition metal ions from ethanol solution onN-acyl-N′-benzoylthiourea—modified silica gel. Microchim Acta 127:229–232

    Article  CAS  Google Scholar 

  52. Osman MM, Kholeif SA, Abou Al-Maaty NA, Mahmoud ME (2003) Metal sorption, solid phase extraction and preconcentration properties of two silica gel phases chemically modified with 2-hydroxy-1-naphthaldehyde. Microchim Acta 143:25–31

    Article  CAS  Google Scholar 

  53. Peng Y, Li Z, Niu Z, Liu Y, Zeng X, Luo Q, Hughes DL, Liu X (2009) Synthesis, characterisation of a complex of Cu(II) with a multidentate marcocyclic ligand and its interactions with anions. Inorg ChimActa 362:3975–3981

    Article  CAS  Google Scholar 

  54. Efimov AM, Pogareva VG, Shashkin AV (2003) Water-related bands in the IR absorption spectra of silicate glasses. J Non-Cryst Solids 332:93–114

    Article  CAS  Google Scholar 

  55. Magyar JS, Weng TC, Stern CM, Dye DF, Rous BW, Payne JC, Bridgewater BM, Mijovilovich A, Parkin G, Zaleski JM, Penner-Hahn JE, Godwin HA (2005) Reexamination of lead(II) coordination preferences in sulfur-rich sites: Implications for a critical mechanism of lead poisoning. J Am Chem Soc 127:9495–9505

    Article  CAS  Google Scholar 

  56. Ngeontae W, Aeungmaitrepirom W, Tuntulani T (2007) Chemically modified silica gel with aminothioamidoanthraquinone for solid phase extraction and preconcentration of Pb(II), Cu(II), Ni(II), Co(II) and Cd(II). Talanta 71:1075–1082

    Article  CAS  Google Scholar 

  57. Fan J, Wu C, Xu H, Wang J, Peng C (2008) Chemically functionalized silica gel with alizarin violet and its application for selective solid-phase extraction of lead from environmental samples. Talanta 74:1020–1025

    Article  CAS  Google Scholar 

  58. Zaporozhets O, Gawer O, Sukhan V (1999) The interaction of Fe (II), Cu (II) and Ag (I) ions and their complexes with 1, 10-phenanthroline adsorbed on silica gel. Colloids Surf A 147:273–281

    Article  CAS  Google Scholar 

  59. Liu P, Pu QS, Sun QY, Su ZX (2000) Synthesis of rhodanine-bonded silica gel and its application in the preconcentration and separation of noble metals. Fresenius J Anal Chem 366:816–820

    Article  CAS  Google Scholar 

  60. Absalan G, Akhond M, Ghanizadeh AZ, Abedi ZA, Tamami B (2007) Benzil derivative of polyacrylohydrazide as a new sorbent for separation, preconcentration and measurement of silver(I) ion. Sep Purif Technol 56:231–236

    Article  CAS  Google Scholar 

  61. Zaporozhets O, Gawer O, Sukhan V (1998) Determination of Fe(II), Cu(II) and Ag(I) by using silica gel loaded with 1, 10-phenanthroline. Talanta 46:1387–1394

    Article  CAS  Google Scholar 

  62. Hassanien MA, Abou-El-Sherbini KS (2006) Synthesis and characterisation of morin-functionalised silica gel for the enrichment of some precious metal ions. Talanta 68:1550–1559

    Article  CAS  Google Scholar 

  63. Zhang S, Pu Q, Liu P, Sun Q, Su Z (2002) Synthesis of amidinothioureido-silica gel and its application to flame atomic absorption spectrometric determination of silver, gold and palladium with on-line preconcentration and separation. Anal Chim Acta 452:223–230

    Article  CAS  Google Scholar 

  64. Ekinci C, Köklü Ü (2000) Determination of vanadium, manganese, silver and lead by graphite furnace atomic absorption spectrometry after preconcentration on silica-gel modified with 3-aminopropyltriethoxysilane. Spectrochim Acta Part B 55:1491–1495

    Article  Google Scholar 

  65. Saad B, Chong CC, Ali ASM, Bari MF, Rahman IA, Mohamad N, Saleh MI (2006) Selective removal of heavy metal ions using sol-gel immobilized and SPE-coated thiacrown ethers. Anal Chim Acta 555:146–156

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank the Education Department of Jiangxi Province (China) and the Program for Innovative Research Team of Nanchang University for financial supports. We also thank our colleague, Professor Fangying Wu, for her helpful discussion.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Lei Li or Xiaoming Liu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 1335 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Peng, Y., Li, Z., Zeng, Y. et al. Solid phase extractors derived by functionalising sub-micro silica gel with chelating agents and their pH-tunable adsorbing capability towards Pb(II) and Ag(I). Microchim Acta 170, 17–26 (2010). https://doi.org/10.1007/s00604-010-0362-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00604-010-0362-9

Keywords

Navigation