Separation/Enrichment of Copper and Silver Using Titanium Dioxide Nanoparticles Coated with Poly-Thiophene and Their Analysis by Flame Atomic Absorption Spectrophotometry


We report on the use of titanium dioxide nanoparticles (NPs) coated with poly-thiophene for the preconcentration of copper and silverions. The NPs were prepared by first modifying the surface of TiO2 NPs with vinyl groups and then copolymerizing them with vinyl thiophen. The resulting TiO2-polythiophene core-shell NPs were characterized by thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X-ray diffraction. The experimental conditions such as pH value, adsorption and desorption time, type, concentration and volume of the eluent, break through volume, and effect of potentially interfering ions were optimized. The ions were then desorbed with hydrochloric acid and determined by FAAS. The limits of detection are 0.4 and 1.2 μg·L_1 for Cu(II) and Ag(I), respectively, and recoveries and precisions are >98.0% and <4%.

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M. Behbahani, M. Babapour, M. Amini, O. Sadeghi, A. Bagheri, M. Salarian and B. Rafiee, "Separation/Enrichment of Copper and Silver Using Titanium Dioxide Nanoparticles Coated with Poly-Thiophene and Their Analysis by Flame Atomic Absorption Spectrophotometry," American Journal of Analytical Chemistry, Vol. 4 No. 2, 2013, pp. 90-98. doi: 10.4236/ajac.2013.42012.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] M. Jamil, M. S. Zia and M. Qasim, “Contamination of Agro-Ecosystem and Human Health Hazards from Waste water Used for Irrigation,” Journal of the Chemical Society of Pakistan, Vol. 32, No. 3, 2010, pp. 370-378.
[2] S. Khan, Q. Cao, Y. M. Zheng, Y. Z. Huang and Y. G. Zhu, “Health Risks of Heavy Metals in Contaminated Soils and Food Crops Irrigated with Wastewater in Beijing,” Environmental Pollution, Vol. 152, No. 3, 2008, pp. 686-692. doi:10.1016/j.envpol.2007.06.056
[3] S.O. Lesmana, N. Febriana, F. E. Soetaredjo, J. Sunarso and S. Ismadji, “Studies on Potential Applications of Bio mass for the Separation of Heavy Metals from Water and Wastewater,” Biochemical Engineering Journal, Vol. 44, No. 1, 2009, pp. 19-41. doi:10.1016/j.bej.2008.12.009
[4] B. Debelius, J. M. Forja, A. D. Valls and L. M. Lubian, “Toxicity and Bioaccumulation of Copper and Lead in Five Marine Microalgae,” Ecotoxicology and Environ mental Safety, Vol. 72, No. 5, 2009, pp. 1503-1513. doi:10.1016/j.ecoenv.2009.04.006
[5] B. G. Wei and L. S. Yang, “A Review of Heavy Metal Contaminations in Urban Soils, Urban Road Dusts and Agricultural Soils from China,” Microchemical Journal, Vol. 94, No. 2, 2010, pp. 99-107. doi:10.1016/j.microc.2009.09.014
[6] F. L. Fu and Q. Wang, “Removal of Heavy Metal Ions from Wastewaters: A Review,” Journal of Environmental Management, Vol. 92, No. 3, 2011, pp. 407-418. doi:10.1016/j.jenvman.2010.11.011
[7] WHO, “Guidelines for Drinking Water Quality, Chemical Facts Sheets,” 2003.
[8] S. Mohan and G. Sreelakshmi, “Fixed Bed Column Study for Heavy Metal Removal Using Phosphate Treated Rice Husk,” Journal of Hazardous Materials, Vol. 153, No. 1 2, 2008, pp. 75-82. doi:10.1016/j.jhazmat.2007.08.021
[9] M. Schaefer and G. D. Gitlin, “Genetic Disorders of Membrane Transport. IV. Wilson’s Disease and Menkes Disease,” The American Journal of Physiology, Vol. 276, No. 2, 1999, pp. 311-314.
[10] S. S. Saei-Dehkordi and A. A. Fallah, “Determination of Copper, Lead, Cadmium and Zinc Content in Commer cially Valuable Fish Species from the Persian Gulf Using Derivative Potentiometric Stripping Analysis,” Micro chemical Journal, Vol. 98, No. 1, 2011, pp. 156-162. doi:10.1016/j.microc.2011.01.001
[11] J. C. Cypriano, M. A. C. Matos and R. C. Matos, “Ultra sound-Assisted Treatment of Palm Oil Samples for the Determination of Copper and Lead by Stripping Chro nopotentiometry,” Microchemical Journal, Vol. 90, No. 1, 2008, pp. 26-30. doi:10.1016/j.microc.2008.03.001
[12] M. Mazloum-Ardakani, Z. Akrami, H. Kazemian and H. R. Zare, “Preconcentration and Electroanalysis of Copper at Zeoilte Modified Carbon Paste Electrode,” Interna tional Journal of Electrochemical Science, Vol. 4, No. 2, 2009, pp. 308-319.
[13] A. Tobiasz, S. Walas, L. Landowska and J. Konefa?-Goral, “Improvement of Copper FAAS Determination Conditions via Preconcentration Procedure with the Use of Sali cylaldoxime Complex Trapped in Polymer Matrix,” Ta lanta, Vol. 96, No. 4, 2012, pp. 82-88. doi:10.1016/j.talanta.2012.02.005
[14] P. C. Bull and D. W. Cox, “Wilson Disease and Menkes Disease: New Handles on Heavy-Metal Transport,” Trends in Genetics, Vol. 10, No. 7, 1994, pp. 246-252. doi:10.1016/0168-9525(94)90172-4
[15] B. Halford, “Ladder Polyethers in a Snap,” Chemical & Engineering News, Vol. 84, No. 3, 2006, pp. 35-36.
[16] S. Morrissey, “Reclassifying Nanosilver,” Chemical & Engineering News, Vol. 84, No. 49, 2006, pp. 14-20.
[17] D. Brandt, B. Park, M. Hoang and H. T. Jacobe, “Argyria Secondary to Ingestion of Homemade Silver Solution,” Journal of the American Academy of Dermatology, Vol. 53, No. 2, 2005, pp. S105-S107. doi:10.1016/j.jaad.2004.09.026
[18] A. M. Donia, A. A. Atia and K. Z. Elwakeel, “Recovery of Gold(III) and Silver(I) on a Chemically Modified Chitosan with Magnetic Properties,” Hydrometallurgy, Vol. 87, No. 3-4, 2007, pp. 197-206. doi:10.1016/j.hydromet.2007.03.007
[19] X. Wang, L. Zhang, C. Ma, R. Song, H. Hou and D. Li, “Enrichment and Separation of Silver from Waste Solutions by Metal Ion Imprinted Membrane,” Hydrometallurgy, Vol. 100, No. 1-2, 2009, pp. 82-86. doi:10.1016/j.hydromet.2009.10.006
[20] G. Yang, W. Fen, C. Lei, W. Xiao and H. Sun, “Study on Solid Phase Extraction and Graphite Furnace Atomic Absorption Spectrometry for the Determination of Nickel, Silver, Cobalt, Copper, Cadmium and Lead with MCI GEL CHP 20Y as sorbent,” Journal of Hazardous Mate rials, Vol. 162, No. 1, 2009, pp. 44-49. doi:10.1016/j.jhazmat.2008.05.007
[21] U. Divrikli, A. A. Kartal, M. Soylak and L. Elci, “Precon centration of Pb(II), Cr(III), Cu(II), Ni(II) and Cd(II) Ions in Environmental Samples by Membrane Filtration Prior to Their Flame Atomic Absorption Spectrometric Deter minations,” J Hazard Mater, Vol. 145, No. 3, 2007, pp. 459-464. doi:10.1016/j.jhazmat.2006.11.040
[22] I. Narin, M. Soylak, K. Kayakirilmaz, L. Elci and M. Dogan, “Preparation of a Chelating Resin by Immobilizing 1-(2-pyridylazo) 2-naphtol on Amberlite XAD-16 and Its Application of Solid Phase Extraction of Ni(II), Cd(II), Co(II), Cu(II), Pb(II), and Cr(III) in Natural Water Sam ples,” Analytical Letters, Vol. 36, No. 3, 2003, pp. 641-658.
[23] D. L. Giokas, E. K. Paleologos and M. I. Karayannis, “Single-Sample Cloud Point Determination of Iron, Co balt and Nickel by Flow Injection Analysis Flame Atomic Absorption Spectrometry-Application to Real Samples and Certified Reference Materials,” Journal of Analytical Atomic Spectrometry, Vol. 16, No. 5, 2001, pp. 521-526. doi:10.1039/b010055m
[24] Q. F. Hu, G. Y. Yang, J. H. Yang and J. Y. Yin, “Study on Determination of Iron, Cobalt, Nickel, Copper, Zinc and Manganese in Drinking Water by Solid-Phase Ex traction and RP-HPLC with 2-(2-Quinolinylazo)-5-Di ethylaminophenol as Precolumn Derivatizing Reagent,” Journal of Environmental Monitoring, Vol. 4, No. 6, 2002, pp. 956-959. doi:10.1039/b204874b
[25] P. Kuban, R. Guchardi and P. C. Hauser, “Trace-Metal Analysis with Separation Methods,” TrAC Trends in Ana lytical Chemistry, Vol. 24, No. 3, 2005, pp. 192-198.
[26] V. Camel, “Solid Phase Extraction of Trace Elements,” Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 58, No. 7, 2003, pp. 1177-1233. doi:10.1016/S0584-8547(03)00072-7
[27] Q. F. Hu, G. Y. Yang, Y. Y. Zhao and J. Y. Yin, “Deter mination of Copper, Nickel, Cobalt, Silver, Lead, Cad mium and Mercury Ions in Water by Solid Phase Extrac tion and the RP-HPLC with UV-Vis Detection,” Analyti cal Bioanalytical Chemistry, Vol. 375, No. 6, 2003, pp. 831-837.
[28] K. Pyrzynska, “Application of Carbon Sorbents for the Concentration and Separation of Metal Ions,” Analytical Sciences, Vol. 23, No. 6, 2007, pp. 631-637. doi:10.2116/analsci.23.631
[29] Q. F. Hu, X. J. Yang, Z. J. Huang, J. Chen and G. Y. Yang, “Simultaneous Determination of Palladium, Plati num, Rhodium and Gold by On-Line Solid Phase Extrac tion and High Performance Liquid Chromatography with 5-(2-Hydroxy-5-Nitrophenylazo) Thiorhodanine as Pre Column Derivatization Regents,” Journal of Chromatography A, Vol. 1094, No. 1-2, 2005, pp. 77-82. doi:10.1016/j.chroma.2005.07.090
[30] A. A. Ensafi, T. Khayamian and M. H. Karbasi, “On-Line Preconcentration System for Lead(II) Determination in Wastewater by Atomic Absorption Spectrometry Using Active Carbon Loaded with Pyrogallol Red,” Analytical Sciences, Vol. 19, No. 6, 2003, pp. 953-956. doi:10.2116/analsci.19.953
[31] M. K. Rofouei, M. Payehghadr, M. Shamsipur and A. Ahmadalinezhad, “Solid Phase Extraction of Ultra Traces Silver(I) Using Octadecyl Silica Membrane Disks Modi fied by 1,3-Bis(2-Cyanobenzene) Triazene (CBT) Ligand Prior to Determination by Flame Atomic Absorption,” Journal of Hazardous Materials, Vol. 168, 2009, pp. 1184-1187. doi:10.1016/j.jhazmat.2009.02.165
[32] B. B. Johnson, “Effect of pH, Temperature, and Concen tration on the Adsorption of Cadmium on Goethite,” En vironmental Science & Technology, Vol. 24, No. 1, 1990, pp. 112-118. doi:10.1021/es00071a014
[33] X. C. Yu, P. F. Zhu, Y. X. Chen, J. Wang and Z. F. An, “Study on Preparation of Modified Nano-TiO2 and Its Application in Photocatalytic Treatment Wastewater Containing Cd2+,” Advanced Materials Research, Vol. 347 353, No. 8, 2012, pp. 733-737. doi:10.4028/
[34] J. Hu, G. Chen and I. M. C. Lo, “Selective Removal of Heavy Metals from Industrial Wastewater Using Mag hemite Nanoparticle: Performance and Mechanisms,” Jour nal of Environmental Engineering, Vol. 132, No. 7, 2006, pp. 709-715. doi:10.1061/(ASCE)0733-9372(2006)132:7(709)
[35] H. J. Shipley, S. Yean, A. T. Kan and M. B. Tomson, “Adsorption of Arsenic to Magnetite Nanoparticles: Effect of Particle Concentration, pH, Ionic Strength, and Temperature,” Environmental Toxicology and Chemistry, Vol. 28, No. 3, 2009, pp. 509-515. doi:10.1897/08-155.1
[36] K. Engates and H. Shipley, “Adsorption of Pb, Cd, Cu, Zn, and Ni to Titanium Dioxide Nanoparticles: Effect of Particle Size, Solid Concentration, and Exhaustion,” Environmental Science and Pollution Research, Vol. 18, No. 3, 2011, pp. 386-395. doi:10.1007/s11356-010-0382-3
[37] T. Kasuga, “Formation of Titanium Oxide Nanotubes Using Chemical Treatments and Their Characteristic Properties,” Thin Solid Films, Vol. 496, No. 1, 2006, pp. 141-145. doi:10.1016/j.tsf.2005.08.341
[38] A. H. Liu, M. D. Wie, I. Honma and H. S. Zhou, “Direct Electrochemistry of Myoglobin in Titanate Nanotubes Film,” Analytical Chemistry, Vol. 77, No. 24, 2005, pp. 8068-8074. doi:10.1021/ac051640t
[39] J. Nawrocki, C. Dunlap, A. McCormick and P. W. Carr, “Chromatography Using Ultra-Stable Metal Oxide-Based Stationary Phases for HPLC,” Journal of Chromatogra phy A, Vol. 1028, No. 1, 2004, pp. 1-30. doi:10.1016/j.chroma.2003.11.052
[40] E. Vassileva, I. Proinova and K. Hadjiivanov, “Solid Phase Extraction of Heavy Metal Ions on a High Surface Area Titanium Dioxide (Anatase),” Analyst, Vol. 121, No. 5, 1996, pp. 607-612. doi:10.1039/an9962100607
[41] V. Camel, “Solid Phase Extraction of Trace Elements,” Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 58, No. 7, 2003, pp. 1177-1233. doi:10.1016/S0584-8547(03)00072-7
[42] L. Zhang, D. Ishi, K. Shitou, Y. Morita and A. Isozaki, “Simultaneous Multi-Element Analysis of Total As, Se and Sb on Titanium Dioxide by Slurry Sampling—Gra phite Furnace Atomic Absorption Spectrometry,” Talanta, Vol. 68, No. 2, 2005, pp. 336-342. doi:10.1016/j.talanta.2005.08.072
[43] M. H. Pinkse, P. M. Uitto, M. J. Hilhorst, B. Ooms and A. J. R. Heck, “Selective Isolation at the Femtomole Level of Phosphopeptides from Proteolytic Digests Using 2D NanoLCESI-MS/MS and Titanium Oxide Precolumns,” Analytical Chemistry, Vol. 76, No. 14, 2004, pp. 3935 3943. doi:10.1021/ac0498617
[44] B. B. Kefi, L. L. E. Atrache, H. Kochkar and A. Ghorbel, “TiO2 Nanotubes as Solid-Phase Extraction Adsorbent for the Determination of Polycyclic Aromatic Hydrocarbons in Environmental Water Samples,” Journal of Environ mental Sciences, Vol. 23, No. 5, 2011, pp. 860-867. doi:10.1016/S1001-0742(10)60481-0
[45] K. Mehrani, A. Mehrani, M. M. Amini, O. Sadeghi and N. Tavassoli, “Dipyridylamine-Modified Nanoporous Silicas as New Sorbents for the Separation and Pre-Concentration of Palladium,” Microchimica Acta, Vol. 173, No. 3-4, 2011, pp. 521-527. doi:10.1007/s00604-011-0590-7
[46] A. Bagheri, M. Behbahani, M. M. Amini, O. Sadeghi, M. Taghizade, L. Baghayi and M. Salarian, “Simultaneous Separation and Determination of Trace Amounts of Cd(II) and Cu(II) in Environmental Samples Using Novel Di phenylcarbazide Modified Nanoporous Silica,” Talanta, Vol. 89, No. 3, 2012, pp. 455-461. doi:10.1016/j.talanta.2011.12.062

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