Abstract
The monitoring of heavy metal ions particularly in water is important in safeguarding the environment and humans from the toxic effects these metal ions pose. This work describes the synthesis, characterization and electrocatalytic properties of silica-coated iron oxide nanoparticles (Si-NP) in the presence of cobalt or iron phthalocyanines (MPc) for heavy metal (HM) detection. TEM, XRD, XPS and VSM confirmed the successful synthesis of Si-NP with an average diameter of 12.07 nm. The electrochemical sensing properties of MPc/Si-NP-modified glassy carbon electrodes (GCE) were assessed for HM detection. Differential pulse anodic stripping voltammetry (DPASV) studies indicated detection limits that compared positively with the literature. The FePc/Si-NP composite showed the lowest detection limits (S/N = 3) of 3.66, 11.56, 2.28, 4.54 μg L−1 for arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb), respectively. A linear working range of 10–100 μg L−1 was obtained for As3+, Hg2+ and Pb2+ ions while it was between 20 and 100 μg L−1 for Cd2+ ions. Both composites displayed reproducible signals for the simultaneous detection of the HMs for ten consecutive scans. These composites offer a cheap and simplistic sensing device for HM analysis.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Andrade AL, Souza DM, Pereira MC, Fabris JD, Domingues RZ (2009) Synthesis and characterization of magnetic nanoparticles coated with silica through a sol-gel approach. Cerâmica 55:420–424. https://doi.org/10.1590/S0366-69132009000400013
Bahrami A, Besharati-Seidani A, Abbaspour A, Shamsipur M (2015) A highly selective voltammetric sensor for nanomolar detection of mercury ions using a carbon ionic liquid paste electrode impregnated with novel ion imprinted polymeric nanobeads. Mater Sci Eng, C 48:205–212. https://doi.org/10.1016/j.msec.2014.12.005
Bao S, Li K, Ninga P, Peng J, Jin X, Tanga L (2016) Highly effective removal of mercury and lead ions from wastewater by mercaptoamine-functionalised silica-coated magnetic nano-adsorbents: behaviours and mechanisms. Appl Surf Sci 393:457–466. https://doi.org/10.1016/j.apsusc.2016.09.098
Barakat MA (2011) New trends in removing heavy metals from industrial wastewater. Arab J Chem 4:361–377. https://doi.org/10.1016/j.arabjc.2010.07.019
Barilaro D, Barone G, Crupi V, Donato MG, Majolino D, Messina G, Ponterio R (2005) Spectroscopic techniques applied to the characterization of decorated potteries from Caltagirone (Sicily, Italy). J Mol Struct 744:827–831. https://doi.org/10.1016/j.molstruc.2004.11.083
Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652. https://doi.org/10.1063/1.464913
Berndt CC, Khor KA, Lugscheider EF (2001) Thermal spray 2001: new surfaces for a New Millennium. In: Proceedings of the 2nd International Thermal Spray Conference, 28–30 May 2001, Singapore. ASM International
Bhanjana G, Dilbaghi N, Kumar R, Umar A, Kumar S (2015) SnO2 quantum dots as novel platform for electrochemical sensing of cadmium. Electrochim Acta 169:97–102. https://doi.org/10.1016/j.electacta.2015.04.045
Buschow KHJ (2013) Handbook of magnetic materials. Elsevier, Great Britain
Ceken B, Kandaz M, Koca A (2012) Electrochemical metal-ion sensors based on a novel manganese phthalocyanine complex. Synth Met 162:1524–1530. https://doi.org/10.1016/j.synthmet.2012.07.019
Ceylan N, Gümrükçü G, Karaoglan GK, Gül A (2015) Synthesis, characterization, fluorescence spectra and energy transfer properties of a novel unsymmetrical zinc phthalocyanine with peripherally coordinated Ru(II) complex. Synth Met 206:55–60. https://doi.org/10.1016/j.synthmet.2015.05.013
Chen L, Li J (2013) A study of γ-Fe2O3 nanoparticles modified using ZnCl2 during synthesis. Adv Mater Phys Chem 3:31–35. https://doi.org/10.4236/ampc.2013.31A004
Cheng F, Su C, Yang Y, Yeh C, Tsai C, Wu C, Wu M, Shieh D (2005) Characterization of aqueous dispersions of Fe3O4 nanoparticles and their biomedical applications. Biomaterials 26:729–738. https://doi.org/10.1016/j.biomaterials.2004.03.016
Cui H, Yang W, Li X, Zhao H, Yuan Z (2012) An electrochemical sensor based on a magnetic Fe3O4 nanoparticles and gold nanoparticles modified electrode for sensitive determination of trace amounts of arsenic (III). Anal Methods 4:4176–4181. https://doi.org/10.1039/c2ay25913c
Dave PN, Chopda LV (2014) Application of iron oxide nanomaterials for the removal of heavy metals. J Nanotechnol. https://doi.org/10.1155/2014/398569
Devnani H, Rajawat DS, Satsangee SP (2014) Black rice modified carbon paste electrode for the voltammetric determination of Pb(II), Cd(II), Cu(II) and Zn(II). Proc Nat Acad Sci India Sect A Phys Sci 84:361–370. https://doi.org/10.1007/s4001
Feng LY, Cao MH, Ma XY, Zhu YS, Hu CW (2012) Superparamagnetic high-surface-area Fe3O4 nanoparticles as adsorbents for arsenic removal. J Hazard Mater 217:439–446. https://doi.org/10.1016/j.jhazmat.2012.03.073
Fialova D, Kremplova M, Melichar L, Kopel P, Hynek D, Adam V, Kizek R (2014) Interaction of heavy metal ions with carbon and iron based particles. Materials 7(3):2242–2256
Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manage 92:407–418. https://doi.org/10.1016/j.jenvman.2010.11.011
Ghandoor HE, Zidan HM, Khalil MMH, Ismail MIM (2012) Synthesis and some physical properties of magnetite (Fe3O4) nanoparticles. Int J Electrochem Sci 7:5734–5745
Guo X, Yun Y, Shanov VN, Halsall HB, Heineman WR (2011) Determination of trace metals by anodic stripping voltammetry using a carbon nanotube tower electrode. Electroanalysis 23:1252–1259. https://doi.org/10.1002/elan.201000674
Haddad PS, Duarte EL, Baptista MS, Goya GF, Leite CAP, Itri R (2004) Synthesis and characterization of silica-coated magnetic nanoparticles. Surf Colloid Sci 128:232–238. https://doi.org/10.1007/b97092
Jaerup L (2003) Hazards of heavy metal contamination. Br Med Bull 68:167–182. https://doi.org/10.1093/bmb/ldg032
Jiang W, Chen XB, Niu YJ, Pan BC (2012) Spherical polystyrene-supported nano-Fe3O4 of high capacity and low-field separation for arsenate removal from water. J Hazard Mater 243:319–325. https://doi.org/10.1016/j.jhazmat.2012.10.036
Jiang J, Holm N, O’Brien K (2015) Improved anodic stripping voltammetric detection of arsenic (III) Using nanoporous gold microelectrode. ECS J Solid State Sci Technol 4(10):S3024–S3029. https://doi.org/10.1149/2.0061510jss
Koudelkova Z, Syrovy T, Ambrozova P, Moravec Z, Kubac L, Hynek D, Richtera L, Adam V (2017) Determination of zinc, cadmium, lead, copper and silver using a carbon paste electrode and a screen-printed electrode modified with chromium(iii) oxide. Sensors (Basel, Switzerland) 17(8):1832–1846. https://doi.org/10.3390/s17081832
Landaburu-Aguirre J, Pongrácz E, Perämäki P, Keiski RL (2010) Micellar-enhanced ultrafiltration for the removal of cadmium and zinc: use of response surface methodology to improve understanding of process performance and optimization. J Hazard Mater 180:524–534. https://doi.org/10.1016/j.jhazmat.2010.04.066
Laurent S, Forge D, Port M, Roch A, Robic C, Vander Elst L, Muller RN (2008) Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physico-chemical characterizations and biological applications. Chem Rev 108:2064–2110. https://doi.org/10.1021/cr068445e
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789. https://doi.org/10.1103/PhysRevB.37.785
Li P, Jiang EY, Bai HL (2011) Fabrication of ultrathin epitaxial γ-Fe2O3 films by reactive sputtering. J Phys D Appl Phys 44:075003–075008. https://doi.org/10.1088/0022-3727/44/7/075003
Liu X, Ma Z, Xing J, Liu H (2004) Preparation and characterization of amino–silane modified superparamagnetic silica nanospheres. J Magn Magn Mater 270:1–6. https://doi.org/10.1016/j.jmmm.2003.07.006
Lopez JA, González F, Bonilla FA, Zambrano G, Gómez ME (2010) Synthesis and characterization of Fe3O4 magnetic nanofluid. Rev Latinoam Metal Mater 30:60–66
Mack J, Kobayashi N (2011) Low symmetry phthalocyanines and their analogues. Chem Rev 111:281–321. https://doi.org/10.1021/cr9003049
Mahdavi M, Ahmad MB, Haron MJ, Gharayebi Y, Shameli K, Nadi B (2013) Fabrication and characterization of SiO2/(3-Aminopropyl) triethoxysilane-coated magnetite nanoparticles for lead (II) removal from aqueous solution. J Inorg Organomet Polym Mater 23:599–607. https://doi.org/10.1007/s10904-013-9820-2
Manivannan A, Kawasaki R, Tryk DA, Fujishima A (2004) Interaction of Pb and Cd during anodic stripping voltammetric analysis at boron-doped diamond electrodes. Electrochim Acta 49:3313–3318. https://doi.org/10.1016/j.electacta.2004.03.004
Mohammadi A, Barikani M (2014) Synthesis and characterization of superparamagnetic Fe3O4 nanoparticles coated with thiodiglycol. Mater Charact 90:88–93. https://doi.org/10.1016/j.matchar.2014.01.021
Mohan D, Pittman CU (2007) Arsenic removal from water/wastewater using adsorbents—a critical review. J Hazard Mater 142:1–53. https://doi.org/10.1016/j.jhazmat.2007.01.006
Mohsen-Nia M, Montazeri P, Modarress H (2007) Removal of Cu2+ and Ni2+ from wastewater with a chelating agent and reverse osmosis processes. Desalination 217:276–281. https://doi.org/10.1016/j.desal.2006.01.043
Moyo S, Mujuru M, McCrindle RI, Mokgalaka-Matlala N (2011) Environmental implications of material leached from coal. J Environ Monit 13:1488–1494
Neyaz N, Siddiqui WA, Nair KK (2014) Application of surface functionalized iron oxide nanomaterials as nanosorbents in extraction of toxic heavy metals from ground water: a review. Int J Environ Sci 4:472–483. https://doi.org/10.6088/ijes.2014040400004
Nyokong T (1995) Electrochemistry of some second-row transition-metal phthalocyanine complexes. S Afr J Chem 48:23–29
Pereira C, Pereira AM, Quaresma P, Tavares PB, Pereira E, Aráujo JP, Freire C (2010) Superparamagnetic γ-Fe2O3@SiO2 nanoparticles: a novel support for the immobilization of [VO(acac)2]. Dalton Trans 39:2842–2854. https://doi.org/10.1039/B920853D
Rajkumar M, Thiagarajan S, Chen S (2011) Electrochemical detection of arsenic in various water samples. Int J Electrochem Sci 6:3164–3177
Salimi A, Mamkhezri H, Hallaj R, Soltanian S (2008) Electrochemical detection of trace amount of arsenic(III) at glassy carbon electrode modified with cobalt oxide nanoparticles. Sens Actuators B Chem 129(1):246–254
Sattler KD (2016) Handbook of nanophysics: nanoparticles and quantum dots. CRC Press, Florida
Shishehbore MR, Afkhami A, Bagheri H (2011) Salicylic acid functionalized silica-coated magnetite nanoparticles for solid phase extraction and preconcentration of some heavy metal ions from various real samples. Chem Central J 5:1–10. https://doi.org/10.1186/1752-153X-5-41
Soleimani F, Aghaiel H, Gharib F (2008) Hydrolysis of cadmium cation in different ionic strength. J Phys Theor Chem 5:73–78
Stephens PJ, Devlin FJ, Chabalowski CF, Frisch MJ (1994) Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. J Phys Chem 98:11623–11627. https://doi.org/10.1021/j100096a001
Tarley CRT, Santos VS, Baêta BEL, Pereira AC, Kubota LT (2009) Simultaneous determination of zinc, cadmium and lead in environmental water samples by potentiometric stripping analysis (PSA) using multiwalled carbon nanotube electrode. J Hazardous Mater 169:256–262. https://doi.org/10.1016/j.jhazmat.2009.03.077
Tau P, Nyokong T (2006) Synthesis and electrochemical characterisation of α- and β- tetra-substituted oxo(phthalocyaninato) titanium(IV) complexes. Polyhedron 25:1802–1810. https://doi.org/10.1016/j.poly.2005.11.025
Turner DR (1987) Speciation and cycling of arsenic, cadmium, lead and mercury in natural waters, Lead, mercury, cadmium and arsenic in the environment, SCOPE. Wiley, New York
Ullah R, Kumer BM, Mollah YA (2014) Synthesis and characterization of silica coated iron-oxide composites of different ratios. Int J Compos Mater 4:135–145. https://doi.org/10.5923/j.cmaterials.20140402.13
Vosko SH, Wilk L, Nusair M (1980) Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis. Can J Phys 58:1200–1211. https://doi.org/10.1139/p80-159
Wang J, Zheng S, Shao Y, Liu J, Xu Z, Zhu D (2010) Amino-functionalized Fe3O4@SiO2 core–shell magnetic nanomaterial as a novel adsorbent for aqueous heavy metals removal. J Colloid Interface Sci 349:293–299. https://doi.org/10.1016/j.jcis.2010.05.010
Wei Y, Yang R, Yu XY, Wang L, Liu JH, Huang XJ (2012) Stripping voltammetry study of ultra-trace toxic metal ions on highly selectively adsorptive porous magnesium oxide nanoflowers. Analyst 137(9):2183
Wu W, He Q, Jiang C (2008) Magnetic iron oxide nanoparticles: synthesis and surface functionalization strategies. Nanoscale Res Lett 3:397–415. https://doi.org/10.1007/s11671-008-9174-9
Wu W, Xiao XH, Zhang SF, Peng TC, Zhou J, Ren F, Jiang CZ (2010) Synthesis and magnetic properties of maghemite γ-Fe2O3 short-nanotubes. Nanoscale Res Lett 5:1474–1479. https://doi.org/10.1007/s11671-010-9664-4
Wu Z, Jiang L, Zhu Y, Xu C, Ye Y, Wang X (2012) Synthesis of mesoporous NiO nanosheet and its application on mercury (II) sensor. J Solid State Electrochem 16(10):3171–3177
Yamada D, Ivandini TA, Komatsu M, Fujishima A, Einaga Y (2008) Anodic stripping voltammetry of inorganic species of As3+ and As5+ at gold-modified boron doped diamond electrodes. J Electroanal Chem 615:145–153. https://doi.org/10.1016/j.jelechem.2007.12.004
Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254:2441–2449. https://doi.org/10.1016/j.apsusc.2007.09.063
Yao X-Z, Guo Z, Yuan Q-H, Liu Z-G, Liu J-H, Huang X-J (2014) Exploiting differential electrochemical stripping behaviors of Fe3O4 nanocrystals toward heavy metal ions by crystal cutting. Appl Mater Interfaces 6:12203–12213. https://doi.org/10.1021/am501617a
Yean S, Cong L, Yavuz CT, Mayo JT, Yu WW (2005) Effect of magnetite particle size on adsorption and desorption of arsenite and arsenate. J Mater Res 20:3255–3264. https://doi.org/10.1557/jmr.2005.0403
Young JG, Onyebuagu W (1990) Synthesis and characterization of di-disubstituted phthalocyanines. J Org Chem 55:2155–2159. https://doi.org/10.1021/jo00294a032
Yu BY, Kwak S (2010) Assembly of magnetite nanoparticles into spherical mesoporous aggregates with a 3-D wormhole-like porous structure. J Mater Chem 20:8320–8328. https://doi.org/10.1039/c0jm01274b
Zhai Y, He Q, Han Q, Duan S (2012) Solid-phase extraction of trace metal ions with magnetic nanoparticles modified with 2,6-diaminopyridine. Microchim Acta 178:405–412. https://doi.org/10.1007/s00604-012-0857-7
Zhao D, Guo X, Wang T, Alvarez N, Shanov VN, Heineman WR (2014) Simultaneous detection of heavy metals by anodic stripping voltammetry using carbon nanotube thread. Electroanalysis 26:488–496. https://doi.org/10.1002/elan.201300511
Zhu L, Xu L, Huang B, Jia N, Tan L, Yao S (2014) Simultaneous determination of Cd (II) and Pb(II) using square wave anodic stripping voltammetry at a gold nanoparticle-graphene-cysteine composite modified bismuth film electrode. Electrochim Acta 115:471–477. https://doi.org/10.1016/j.electacta.2013.10.209
Acknowledgements
The authors would like to thank the National Research Foundation of South Africa for the Thuthuka research Grant.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Gounden, D., Khene, S. & Nombona, N. Electroanalytical detection of heavy metals using metallophthalocyanine and silica-coated iron oxide composites. Chem. Pap. 72, 3043–3056 (2018). https://doi.org/10.1007/s11696-018-0545-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-018-0545-0