Ferrocenium tetrachloromagnesate modified MWCNTs electrode for detection of Bi3+ at the trace level in polluted aqueous solutions

Original scientific paper

Authors

  • Rahadian Zainul Department of Chemistry, Faculty of Natural Science and Mathematics, Universitas Negeri Padang, 25132 Air Tawar, Padang, Indonesia https://orcid.org/0000-0002-3740-3597
  • Alwi Nofriandi Doctoral Program of Environmental Science, Postgraduate Program, Universitas Negeri Padang, 25132 Air Tawar, Padang Indonesia https://orcid.org/0009-0006-4254-3080
  • Norhayati Hashim Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0001-7095-8597
  • Mohamad Idris Saidin Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0001-9735-7150
  • Mohamad Syahrizal Ahmad Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0002-9278-6332
  • Siti Nur Akmar Mohd Yazid Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0002-9867-5641
  • Sharifah Norain Mohd Sharif Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0002-2869-9787
  • Wan Rusmawati Wan Mahamod Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0003-1885-1893
  • Illyas Md Isa Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak, Malaysia https://orcid.org/0000-0002-7621-2929

DOI:

https://doi.org/10.5599/jese.3085

Keywords:

Magnesium containing complex, organometallic compound, electroactive modifier, heavy metal detection, environmental (water) samples

Abstract

This study presents the fabrication of a ferrocenium tetrachloromagnesate (FTM) modified multi-walled carbon nanotubes (MWCNTs) electrode for the voltammetric determination of bismuth ions (Bi3+) in aquatic environments. The FTM was synthesized from the reaction of mag­nesium chloride with ferrocene. The incorporation of FTM, a redox-active species, was shown to markedly improve electron transfer kinetics and overall electrochemical conductivity. Structural and morphological characterizations via Fourier transform infrared spectroscopy, transmission electron microscopy, energy dispersive x-ray, field emission scanning electron microscopy and X-ray diffraction confirmed the successful embedding of FTM within the electrode matrix. Electrochemical assessments using cyclic voltammetry, electrochemical impe­dance spectro­scopy, and chronocoulometry revealed that a 10 wt.% FTM loading provided the most optimal charge transfer and interfacial behaviour. Differential pulse stripping voltammetry further demonstrated the high sensitivity of the developed electrode, achieving an ultralow detection limit of 0.543 nM with two broad linear ranges of 1.0 nM to 0.1 and 1.0 µM to 0.1 mM for Bi3+. The sensor also exhibited remarkable reproducibility (RSD 8.67 %) and stability (RSD 7.77 %). Furthermore, excellent selectivity toward Bi3+ was maintained in the presence of potentially interfering ions such as Mn2+, La3+, Ni2+, Li+, Zn2+, Fe2+, Cd2+, Cu2+, Er2+ and Pb2+. Real water-sample analyses yielded recoveries of 89 to 104 %, confirming the practical feasibility of the electrode for environmental monitoring.

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References

[1] H. Li, B. Cheng, J. Zhang, X. Zhou, C. Shi, L. Zeng, C. Wang, Recent advances in the application of bismuth-based catalysts for degrading environmental emerging organic contaminants through photocatalysis, Journal of Environmental Chemical Engineering 11 (2023) 110371. https://doi.org/10.1016/j.jece.2023.110371 DOI: https://doi.org/10.1016/j.jece.2023.110371

[2] M. Zacchini, Bismuth interaction with plants: Uptake and transport, toxic effects, tolerance mechanisms, Chemosphere 360 (2024) 142414. https://doi.org/10.1016/j.chemosphere.2024.142414 DOI: https://doi.org/10.1016/j.chemosphere.2024.142414

[3] S. A. Shetu, L. M. Sanchez-Palestino, G. Rivera, D. Bandyopadhyay, Medicinal bismuth: Bismuth-organic frameworks as pharmaceutically privileged compounds, Tetrahedron 129 (2022) 133117. https://doi.org/10.1016/j.tet.2022.133117 DOI: https://doi.org/10.1016/j.tet.2022.133117

[4] M. Fadhlaoui, N.J.T. Pearce, I. Lavoie, C. Fortin, Interactive effects of bismuth exposure (water and diet) and temperature on snail fatty acid composition, antioxidant enzymes and lipid peroxidation, Frontiers in Environmental Chemistry 5 (2024) 1332967. https://doi.org/10.3389/fenvc.2024.1332967 DOI: https://doi.org/10.3389/fenvc.2024.1332967

[5] F. Pietrini, L. Passatore, S. Carloni, L. Massimi, M. L. Astolfi, C. Giusto, M. Zacchini, Bismuth exposure affects morpho-physiological performances and the ionomic profile in garden cress (Lepidium sativum L.) plants, Frontiers in Environmental Science 11 (2023) 1221573. https://doi.org/10.3389/fenvs.2023.1221573 DOI: https://doi.org/10.3389/fenvs.2023.1221573

[6] S. Kolesnikov, T. Minnikova, K. Kazeev, Y. Akimenko, N. Evstegneeva, Assessment of the ecotoxicity of pollution by potentially toxic elements by biological indicators of Haplic Chernozem of Southern Russia (Rostov region), Water, Air, & Soil Pollution 233 (2022) 18. https://doi.org/10.1007/s11270-021-05496-3 DOI: https://doi.org/10.1007/s11270-021-05496-3

[7] S. Gavrilaș, F. L. Burescu, B. D. Chereji, F. D. Munteanu, The Impact of anthropogenic activities on the catchment’s water quality parameters, Water 17 (2025) 1791. https://doi.org/10.3390/w17121791 DOI: https://doi.org/10.3390/w17121791

[8] D. S. Chormey, E. Ö. Er, S. E. Bodur, B. T. Zaman, S. Bodur, T. B. Kustanto, İ. Kayın, S. Bakırdere, Trace element determination using mass spectrometry coupled detection methods, Trends in Environmental Analytical Chemistry 45 (2025) e00257. https://doi.org/10.1016/j.teac.2024.e00257 DOI: https://doi.org/10.1016/j.teac.2024.e00257

[9] R. Lindenmayer, L. Lu, F. Eivazi, Z. Afrasiabi, Atomic spectroscopy-based analysis of heavy metals in seaweed species, Applied Sciences 13 (2023) 4764. https://doi.org/10.3390/app13084764 DOI: https://doi.org/10.3390/app13084764

[10] M. Madadelahi, F. O. Romero-Soto, R. Kumar, U. B. Tlaxcala, M. J. Madou, Electrochemical sensors: Types, applications, and the novel impacts of vibration and fluid flow for microfluidic integration, Biosensors and Bioelectronics 272 (2025) 117099. https://doi.org/10.1016/j.bios.2024.117099 DOI: https://doi.org/10.1016/j.bios.2024.117099

[11] A. Shabib, M.A. Maraqa, A.F. Mohammad, F. Awwad, Design, fabrication, and application of electrochemical sensors for microplastic detection: a state-of-the-art review and future perspectives, Environmental Sciences Europe 37 (2025) 94. https://doi.org/10.1186/s12302-025-01138-1 DOI: https://doi.org/10.1186/s12302-025-01138-1

[12] A. Nofriandi, I. Isa, N. Hashim, M. Idris, M. Syahrizal, I. Dewata, Ultrasensitive voltammetric sensor based on ferrocenium tetrachloroferrate for determination of manganese(II) in water pollutant, Materials Chemistry and Physics 339 (2025) 130725. https://doi.org/10.1016/j.matchemphys.2025.130725 DOI: https://doi.org/10.1016/j.matchemphys.2025.130725

[13] X. Zhou, Electrochemical detection of heavy metal ions in water using MWCNT/ZnO nanocomposite, International Journal of Electrochemical Science 19 (2024) 100559. https://doi.org/10.1016/j.ijoes.2024.100559 DOI: https://doi.org/10.1016/j.ijoes.2024.100559

[14] P. J. Obeid, N. Sari-Chmayssem, P. Yammine, D. Homsi, H. El-Nakat, Z. Matar, S. Hamieh, D. Koumeir, A. Chmayssem, Designs and materials of electrodes for electrochemical sensors, ChemElectroChem 12 (2025) e202500230. https://doi.org/10.1002/celc.202500230 DOI: https://doi.org/10.1002/celc.202500230

[15] R. Singh, R. Gupta, D. Bansal, R. Bhateria, M. Sharma, A Review on recent trends and future developments in electrochemical sensing, ACS Omega 9 (2023) 7336-7356. https://doi.org/10.1021/acsomega.3c08060 DOI: https://doi.org/10.1021/acsomega.3c08060

[16] M. Mulyawati, K. A. Madurani, I. Ulfin, N. P. Sari, F. Kurniawan, Development of a copper-modified iron electrode electrochemical sensor for sensitive detection of oxalic acid, Materials Chemistry and Physics 344 (2025) 131063. https://doi.org/10.1016/j.matchemphys.2025.131063 DOI: https://doi.org/10.1016/j.matchemphys.2025.131063

[17] J. Kim, J. Ling, Y. Lai, P.J. Milner, Redox-active organic materials: From energy storage to redox catalysis, ACS Materials Au 4 (2024) 258-273. https://doi.org/10.1021/acsmaterialsau.3c00096 DOI: https://doi.org/10.1021/acsmaterialsau.3c00096

[18] X. Du, Z. Lin, X. Wang, K. Zhang, H. Hu, S. Dai, Electrode materials, structural design, and storage mechanisms in hybrid supercapacitors, Molecules 28 (2023) 6432. https://doi.org/10.3390/molecules28176432 DOI: https://doi.org/10.3390/molecules28176432

[19] D. V. Estrada-Osorio, R. A. Escalona-Villalpando, A. Gutiérrez, L. G. Arriaga, J. Ledesma-García, Poly-L-lysine-modified with ferrocene to obtain a redox polymer for mediated glucose biosensor application, Bioelectrochemistry 146 (2022) 108147. https://doi.org/10.1016/j.bioelechem.2022.108147 DOI: https://doi.org/10.1016/j.bioelechem.2022.108147

[20] S. Nuthana Kalva, F. Ali, M. Koç, Recent advances in the post-processing of magnesium based scaffolds for orthopedic applications, Next Materials 6 (2025) 100295. https://doi.org/10.1016/j.nxmate.2024.100295 DOI: https://doi.org/10.1016/j.nxmate.2024.100295

[21] V. Tsakiris, C. Tardei, F. M. Clicinschi, Biodegradable Mg alloys for orthopedic implants - A review, Journal of Magnesium and Alloys 9 (2021) 1884-1905. https://doi.org/10.1016/j.jma.2021.06.024 DOI: https://doi.org/10.1016/j.jma.2021.06.024

[22] J. Xie, T. Zhang, J. Jiang, W. Xue, W. Wang, J. Ni, X. Zhang, X. Liu, Advances in magnesium-based implants for biomedical applications: A comprehensive review and future perspectives, Journal of Magnesium and Alloys 13 (2025) 2978-3003. https://doi.org/10.1016/j.jma.2025.05.009 DOI: https://doi.org/10.1016/j.jma.2025.05.009

[23] H. Strzelecka-Gołaszeska, A. Woźniak, T. Hult, U. Lindberg, Effects of the type of divalent cation, Ca2+ or Mg2+, bound at the high-affinity site and of the ionic composition of the solution on the structure of F-actin, Biochemical Journal 316 (1996) 713-721. https://doi.org/10.1042/bj3160713 DOI: https://doi.org/10.1042/bj3160713

[24] Y. Luo, L. Liu, H. Wang, T. Liu, H. Li, B. Tan, Y. Pan, A. Liu, J. Cheng, Research progress on the corrosion behavior of magnesium alloys in natural environments, Materials Today Communications 48 (2025) 113433. https://doi.org/10.1016/j.mtcomm.2025.113433 DOI: https://doi.org/10.1016/j.mtcomm.2025.113433

[25] Y. Kang, K. Zhang, X. Lin, Surface modifications of magnesium-based materials for hydrogen storage and nickel-metal hydride batteries, Coatings 13 (2023) 1100. https://doi.org/10.3390/coatings13061100 DOI: https://doi.org/10.3390/coatings13061100

[26] T. Zhang, W. Wang, J. Liu, L. Wang, Y. Tang, K. Wang, A review on magnesium alloys for biomedical applications, Frontiers in Bioengineering and Biotechnology 10 (2022) 953344. https://doi.org/10.3389/fbioe.2022.953344 DOI: https://doi.org/10.3389/fbioe.2022.953344

[27] R. Kumar, S. Kumar, A.J. Kailath, R.K. Sahu, Mechanistic investigation of hydrogen generation from water and magnesium catalyst reaction: Advanced reactive molecular dynamics simulation, International Journal Hydrogen Energy 52 (2024) 1440-1445. https://doi.org/10.1016/j.ijhydene.2023.07.247 DOI: https://doi.org/10.1016/j.ijhydene.2023.07.247

[28] K. K. Thomas, M. N. Zafar, W. G. Pitt, G.A. Husseini, Biodegradable magnesium alloys for bio-medical implants: Properties, challenges, and surface modifications with a focus on orthopedic fixation repair, Applied Sciences 14 (2024) 10. https://doi.org/10.3390/app14010010 DOI: https://doi.org/10.3390/app14010010

[29] S. Mehanathan, J. Jaafar, A. M. Nasir, A. F. Ismail, T. Matsuura, M. H. D. Othman, M. A. Rahman, N. Yusof, Magnesium oxide nanoparticles for the adsorption of pentavalent arsenic from water: Effects of calcination, Membranes 13 (2023) 475. https://doi.org/10.3390/membranes13050475 DOI: https://doi.org/10.3390/membranes13050475

[30] B. Liu, H. Guo, L. Sun, Z. Pan, L. Peng, M. Wang, N. Wu, Y. Chen, X. Wei, W. Yang, Electrochemical sensor based on covalent organic frameworks/MWCNT for simultaneous detection of catechol and hydroquinone, Colloids and Surfaces A 639 (2022) 128335. https://doi.org/10.1016/j.colsurfa.2022.128335 DOI: https://doi.org/10.1016/j.colsurfa.2022.128335

[31] Y. Yulkifli, W. P. Yandes, I. M. Isa, N. Hashim, A. Ulianas, S. N. M. Sharif, M. I. Saidin, M. S. Ahmad, S. N. A. M. Yazid, S. Suyanta, R. Nuryadi, N. Abd Azis, A nanocomposite paste electrode sensor for simultaneous detection of uric acid and bisphenol A using zinc hydroxide nitrate-sodium dodecylsulfate Bispyribac, Sensors 23 (2023) 8366. https://doi.org/10.3390/s23208366 DOI: https://doi.org/10.3390/s23208366

[32] L. Johansson, K. Haugsten, H. H. Bruun, O. Smidsrød, A. A. Lindberg, G. Jansen, B. Lamm, B. Samuelsson, The complex formation of bismuth(III) with chloride in aqueous solution. A solubility study., Acta Chemica Scandinavica 23 (1969) 548-556. https://doi.org/10.3891/acta.chem.scand.23-0548 DOI: https://doi.org/10.3891/acta.chem.scand.23-0548

[33] V. Baibakova, K. Cruse, M. G. Taylor, C. M. Sutter-Fella, G. Ceder, A. Jain, S. M. Blau, Precursor reaction pathway leading to BiFeO3 formation: insights from text-mining and chemical reaction network analyses, Digital Discovery 4 (2025) 1602-1611. https://doi.org/10.1039/d5dd00160a DOI: https://doi.org/10.1039/D5DD00160A

[34] H. Bhatia, J. Guo, C. N. Savory, M. Rush, D. I. James, A. Dey, C. Chen, D. K. Bučar, T. M. Clarke, D. O. Scanlon, R. G. Palgrave, B. C. Schroeder, Exploring bismuth coordination complexes as visible-light absorbers: Synthesis, characterization, and photophysical properties, Inorganic Chemistry 63 (2024) 416-430. https://doi.org/10.1021/acs.inorgchem.3c03290 DOI: https://doi.org/10.1021/acs.inorgchem.3c03290

[35] X. S. Wang, A. E. Williams-Jones, R. Z. Hu, Q. Liu, F. X. Liu, Y. Mei, Z. Q. Jiang, L. B. Shang, J.J. Zhu, X. W. Bi, The transport of bismuth in HCl-bearing aqueous vapour and low-density aqueous supercritical fluids: Implications for natural systems, Geochimica et Cosmochimica Acta 378 (2024) 203-216. https://doi.org/10.1016/j.gca.2024.06.008 DOI: https://doi.org/10.1016/j.gca.2024.06.008

[36] K. Yamashita, K. Komatsu, H. Kagi, Crystal structure of potassium chloride monohydrate: water intercalation into the B1 structure of KCl under high pressure, Acta Crystallographica Section C 78 (2022) 749-754. https://doi.org/10.1107/S2053229622011135 DOI: https://doi.org/10.1107/S2053229622011135

[37] D. B. Kleja, J. P. Gustafsson, V. Kessler, I. Persson, Bismuth(III) forms exceptionally strong complexes with natural organic matter, Environmental Science & Technology 56 (2022) 3076-3084. https://doi.org/10.1021/acs.est.1c06982 DOI: https://doi.org/10.1021/acs.est.1c06982

[38] A. H. Alanazi, A. S. Al-zbedy, R. El-sayed, K. F. Debbabi, A. S. Amin, A. S. Al-zbedy, Eco-friendly optical sensor for detecting bismuth(III) ions in environmental , pharmaceutical , and biological sources, Chinese Journal of Analytical Chemistry 53 (2025) 100591. https://doi.org/https://doi.org/10.1016/j.cjac.2025.100591 DOI: https://doi.org/10.1016/j.cjac.2025.100591

[39] Y. Jiang, D. Tai, Z. Xiao, J. Liu, Ratiometric luminescence detection of Bi3+ ions in water using a europium coordination polymer, Spectroscopy Letters 58 (2025) 445-452. https://doi.org/10.1080/00387010.2024.2447519 DOI: https://doi.org/10.1080/00387010.2024.2447519

[40] R.F. Aglan, M.M. Hamed, H.M. Saleh, A new screen-printed electrode for selective determination of bismuth in different authentic samples, Journal of the Iranian Chemical Society 20 (2023) 1481-1490. https://doi.org/10.1007/s13738-023-02771-4 DOI: https://doi.org/10.1007/s13738-023-02771-4

[41] N. Sharma, A. Sharma, M. Park, H.J. Lee, Silkworm-derived carbon nano rods (swCNR) for detection of bismuth ions (Bi3+) in aquatic medium and their antiradical properties, Heliyon 10 (2024) e33572. https://doi.org/10.1016/j.heliyon.2024.e33572 DOI: https://doi.org/10.1016/j.heliyon.2024.e33572

[42] Z. Smanova, B. Normatov, U. Ahmadjonov, S. Rakhimov, B. Shodmonov, E. Berdimurodov, W. M. N. B Wan Nik, I. Eliboev, G. K. Ziyayeva, O. Baigenzhenov, A. Hosseini-Bandegharaei, Sorption-spectrophotometric determination of bismuth ion (III) using immobilised xylenol orange on modified polyacrylonitrile, International Journal of Environmental Analytical Chemistry 105 (2025) 58595879. https://doi.org/10.1080/03067319.2024.2405067 DOI: https://doi.org/10.1080/03067319.2024.2405067

[43] J. A. Rajabi-Orhani, L. Dolatyari, M. Reza Yaftian, A different application of the Aliquat® 336 loaded poly(vinylidene fluoride-co-hexafluoropropylene) based electrospun nanofibers disks for the preconcentration followed by flame atomic absorption spectrometry detection of low-level Bi3+, Microchemical Journal 207 (2024) 111703. https://doi.org/10.1016/j.microc.2024.111703 DOI: https://doi.org/10.1016/j.microc.2024.111703

[44] Anoushka, M. Rani, U. Shanker, Rapid microwave assisted synthesis of N-doped CQDs for highly selective ‘turn-off’ sensing of bismuth(III) ions in wastewater, Analytica Chimica Acta 1351 (2025) 343904. https://doi.org/10.1016/j.aca.2025.343904 DOI: https://doi.org/10.1016/j.aca.2025.343904

[45] L. K. Shaji, J. Jose, R. Bhaskar, R. Selva Kumar, V. Vetriarasu, S. G. Bhat, S. K. Ashok Kumar, Smartphone assisted fluorescent-colorimetric probe for bismuth(III) ion and potential applications, Inorganic Chemistry Communications 147 (2023) 110252. https://doi.org/10.1016/j.inoche.2022.110252 DOI: https://doi.org/10.1016/j.inoche.2022.110252

Published

05-01-2026

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Section

Electroanalytical chemistry

How to Cite

Ferrocenium tetrachloromagnesate modified MWCNTs electrode for detection of Bi3+ at the trace level in polluted aqueous solutions: Original scientific paper. (2026). Journal of Electrochemical Science and Engineering, 16, Article 3085. https://doi.org/10.5599/jese.3085

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