Rapid and sensitive electrochemical determination of phosphate ions using a multi-walled carbon nanotube carbon paste electrode
Original scientific paper
DOI:
https://doi.org/10.5599/jese.3261Keywords:
Phosphate anion sensing, nanomaterial-modified electrode, phosphomolybdate complex, voltammetric methods, real food samplesAbstract
Phosphates are widely used in food as texture modifiers, preservatives and flavour enhancers, while excessive intake may negatively affect human health and the environment. Consequently, there is a growing demand for low-cost, portable, and reliable tools for phosphate monitoring in food and water samples. In this work, an electrochemical sensor based on a multi-walled carbon nanotube (MWCNT) modified carbon paste electrode (CPE) was developed for phosphate determination. Phosphate detection was based on the electrochemical reduction of an electroactive phosphomolybdate complex formed in acidic medium (50 mM sulfuric acid). Key analytical parameters, including solution acidity and complexation time, were optimized to enhance sensor performance. Carbon nanotube modification significantly enhanced the electrochemical response. While the bare CPE shows weak, poorly defined redox peaks due to limited electron transfer and low surface area, MWCNT-modified CPE exhibits well-defined peaks with ~6-fold higher current, reflecting improved sensitivity, faster electron transfer, and better peak separation. Using square-wave voltammetry, the sensor exhibited a linear response in the phosphate concentration range of 3.1 to 21.7 mg L⁻¹, with a detection limit of 0.03 mg L⁻¹ and a response time of approximately 10 s. The sensor was successfully applied to real sausage samples, yielding recoveries of 94.6 to 97.2 % with relative standard deviation values below 5 %. The presented MWCNT-CPE sensor provides a cost-effective, portable and simple device for fast and reliable in situ detection of phosphate in food and water samples.
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References
[1] S. Pourbeyram, M. Soltanpour, S. Fathalipour. Determination of Phosphate in Human Serum with Zirconium/Reduced Graphene Oxide Modified Electrode, Analytical Sciences 35 (2019) 739-743. https://dx.doi.org/10.2116/analsci.18P548 DOI: https://doi.org/10.2116/analsci.18P548
[2] H. Wei, D. Pan, Z. Zhou, H. Han, R. Zhu, On-site electrochemical determination of phosphate with high sensitivity and anti-interference ability in turbid coastal waters, Ecotoxicology and Environmental Safety 221 (2021) 112444. https://dx.doi.org/10.1016/j.ecoenv.2021.112444 DOI: https://doi.org/10.1016/j.ecoenv.2021.112444
[3] J. J. Elser, M. E. Bracken, E. E. Cleland, D. S. Gruner, W. S. Harpole, H. Hillebrand, J. T. Ngai, E. W. Seabloom, J. B. Shurin, J. E. Smith, Global analysis of nitrogen and phosphorus limitation of primary producers in freshwater, marine and terrestrial ecosystems, Ecology Letters 10 (2007) 1135-1142. https://dx.doi.org/10.1111/j.1461-0248.2007.01113.x DOI: https://doi.org/10.1111/j.1461-0248.2007.01113.x
[4] S. Jiang, H. Hua, H. Sheng, H. P. Jarvie, X. Liu, Y. Zhang, Z. Yuan, L. Zhang, X. Liu, Phosphorus footprint in China over the 1961-2050 period: Historical perspective and future prospect, Science of the Total Environment 650 (2019) 687-695. https://dx.doi.org/10.1016/j.scitotenv.2018.09.064 DOI: https://doi.org/10.1016/j.scitotenv.2018.09.064
[5] D. Cordell, J. O. Drangert, S. White, The story of phosphorus: global food security and food for thought, Global Environmental Change 19 (2009) 292-305. https://dx.doi.org/10.1016/j.gloenvcha.2008.10.009 DOI: https://doi.org/10.1016/j.gloenvcha.2008.10.009
[6] V. Smil, Phosphorus in the environment: natural flows and human interferences, Annual Review of Energy and the Environment 25 (2000) 53-88. https://dx.doi.org/10.1146/annurev.energy.25.1.53 DOI: https://doi.org/10.1146/annurev.energy.25.1.53
[7] R. Dupas, M. Delmas, J. M. Dorioz, J. Garnier, F. Moatar, C. Gascuel-Odoux, Assessing the impact of agricultural pressures on N and P loads and eutrophication risk, Ecological Indicators 48 (2015) 396-407. https://dx.doi.org/10.1016/j.ecolind.2014.08.007 DOI: https://doi.org/10.1016/j.ecolind.2014.08.007
[8] D. Talarico, F. Arduini, A. Amine, D. Moscone, G. Palleschi, Screen-printed electrode modified with carbon black nanoparticles for phosphate detection by measuring the electroactive phosphomolybdate complex, Talanta 141 (2015) 267-272. https://dx.doi.org/10.1016/j.talanta.2015.04.006 DOI: https://doi.org/10.1016/j.talanta.2015.04.006
[9] C. Sullivan, S. S. Sayre, J. B. Leon, R. Machekano, T. E. Love, D. Porter, M. Marbury, A. R. Sehgal, Effect of food additives on hyperphosphatemia among patients with end-stage renal disease: a randomized controlled trial, JAMA 301 (2009) 629-635. https://dx.doi.org/10.1001/jama.2009.96 DOI: https://doi.org/10.1001/jama.2009.96
[10] E. Ritz, K. Hahn, M. Ketteler, M. K. Kuhlmann, J. Mann, Phosphate additives in food—A health risk, Deutsches Ärzteblatt International 109 (2012) 49-55. https://dx.doi.org/10.3238/arztebl.2012.0049 DOI: https://doi.org/10.3238/arztebl.2012.0049
[11] M. S. Calvo, E. K. Dunford, J. Uribarri, Industrial Use of Phosphate Food Additives: A Mechanism Linking Ultra-Processed Food Intake to Cardiorenal Disease Risk?, Nutrients 15 (2023) 3510. https://dx.doi.org/10.3390/nu15163510 DOI: https://doi.org/10.3390/nu15163510
[12] M. S. Calvo, R. A. Sherman, J. Uribarri, Dietary Phosphate and the Forgotten Kidney Patient: A Critical Need for FDA Regulatory Action, American Journal of Kidney Diseases 73 (2019) 542-551. https://dx.doi.org/10.1053/j.ajkd.2018.11.004 DOI: https://doi.org/10.1053/j.ajkd.2018.11.004
[13] V. Ruiz-Calero, M. T. Galceran, Ion chromatographic separations of phosphorus species: a review, Talanta 66 (2005) 376-410. https://dx.doi.org/10.1016/j.talanta.2005.01.027 DOI: https://doi.org/10.1016/j.talanta.2005.01.027
[14] L. Kröckel, H. Lehmann, T. Wieduwilt, M. A. Schmidt, Fluorescence detection for phosphate monitoring using reverse injection analysis, Talanta 125 (2014) 107-113. https://dx.doi.org/10.1016/j.talanta.2014.02.072 DOI: https://doi.org/10.1016/j.talanta.2014.02.072
[15] Y. S. Li, Y. Muo, H. M. Xie, Simultaneous determination of silicate and phosphate in boiler water at power plants based on series flow cells by using flow injection spectrophotometry, Analytica Chimica Acta 455 (2002) 315-325. https://dx.doi.org/10.1016/S0003-2670(01)01609-9 DOI: https://doi.org/10.1016/S0003-2670(01)01609-9
[16] N. Nakatani, D. Kozaki, W. Masuda, N. Nakagoshi, K. Hasebe, M. Mori, K. Tanaka, Simultaneous spectrophotometric determination of phosphate and silicate ions in river water, Analytica Chimica Acta 619 (2008) 110-114. https://dx.doi.org/10.1016/j.aca.2008.02.043 DOI: https://doi.org/10.1016/j.aca.2008.02.043
[17] M. S. A. Neves, M. R. S. Souto, I. V. Tóth, S. M. Victal, M. C. Drumond, A. O. Rangel, Spectrophotometric flow system for phosphate determination with improved sensitivity, Talanta 77 (2008) 527-532. https://dx.doi.org/10.1016/j.talanta.2008.03.014 DOI: https://doi.org/10.1016/j.talanta.2008.03.014
[18] S. Berchmans, T. B. Issa, P. Singh, Determination of inorganic phosphate by electroanalytical methods: a review, Analytica Chimica Acta 729 (2012) 7-20. https://dx.doi.org/10.1016/j.aca.2012.03.060 DOI: https://doi.org/10.1016/j.aca.2012.03.060
[19] M. Talbi, A. Anurag, C. Tegenkamp, M. Ben Ali, O. Kanoun, A high-performance reagent-less sensor for phosphate detection, RSC Advances 15 (2025) 8156-8168. https://dx.doi.org/10.1039/d5ra00350d DOI: https://doi.org/10.1039/D5RA00350D
[20] R. Zeitoun, A. Biswas, Potentiometric determination of phosphate using cobalt: A review, Journal of The Electrochemical Society 167 (2020) 127507. https://dx.doi.org/10.1149/1945-7111/ab983f DOI: https://doi.org/10.1149/1945-7111/abad6c
[21] K. Xu, Y. Kitazumi, K. Kano, O. Shirai, Phosphate ion sensor using a cobalt phosphate coated cobalt electrode, Electrochimica Acta 282 (2018) 242-246. https://dx.doi.org/10.1016/j.electacta.2018.06.021 DOI: https://doi.org/10.1016/j.electacta.2018.06.021
[22] M. B. Arvas, O. Gorduk, M. Gencten, Y. Sahin, Preparation of a novel electrochemical sensor for phosphate detection, Analytical Methods 11 (2019) 3874-3881. https://dx.doi.org/10.1039/C9AY01275C DOI: https://doi.org/10.1039/C9AY01275C
[23] K. Xu, Y. Li, M. Li, Potentiometric phosphate ion sensor based on modified tungsten electrode, ACS Omega 6 (2021) 13795-13801. https://dx.doi.org/10.1021/acsomega.1c00195 DOI: https://doi.org/10.1021/acsomega.1c00195
[24] Y. Li, J. Liu, L. Zhang, Q. Yang, W. Chen, J. Wu, L. Zhang, X. Li, K. Xu, Amperometric highly sensitive phosphate ion sensor, Langmuir 40 (2024) 19187-19194. https://dx.doi.org/10.1021/acs.langmuir.4c02342 DOI: https://doi.org/10.1021/acs.langmuir.4c02342
[25] Y. Zhang, T. F. Kang, Y. W. Wan, S. Y. Chen, Gold nanoparticles-carbon nanotubes modified sensor, Microchimica Acta 165 (2009) 307-311. https://dx.doi.org/10.1007/s00604-008-0134-y DOI: https://doi.org/10.1007/s00604-008-0134-y
[26] M. F. Kabir, M. T. Rahman, A. Gurung, Q. Qiao, Electrochemical phosphate sensors using silver nanowires, IEEE Sensors Journal 18 (2018) 3480-3485. https://dx.doi.org/10.1109/JSEN.2018.2808163 DOI: https://doi.org/10.1109/JSEN.2018.2808163
[27] S. R. Sari, M. Tsushida, T. Sato, M. Tominaga, Highly sensitive detection of phosphate using cobalt oxide nanoparticles, Materials Advances 3 (2022) 2018-2025. https://dx.doi.org/10.1039/D1MA01097B DOI: https://doi.org/10.1039/D1MA01097B
[28] S. M. Mugo, W. Lu, S. Lemieux. Stainless steel electrochemical capacitive microneedle sensors, Mikrochimica Acta 189 (2022) 206. https://dx.doi.org/10.1007/s00604-022-05307-4 DOI: https://doi.org/10.1007/s00604-022-05307-4
[29] R. Eivazzadeh-Keihan, E. B. Noruzi, E. Chidar, M. Jafari, F. Davoodi, A. Kashtiaray, M. Mahdavi, Applications of carbon-based conductive nanomaterials in biosensors, Chemical Engineering Journal 442 (2022) 136183. https://dx.doi.org/10.1016/j.cej.2022.136183 DOI: https://doi.org/10.1016/j.cej.2022.136183
[30] H. Moradpour, H. Forootanfar, A. Ameri, H. Beitollahi, Fabrication of enzyme-modified carbon paste electrode for dopamine measurement, International Journal of Biological Macromolecules 283 (2024) 137891. https://dx.doi.org/10.1016/j.ijbiomac.2024.137891 DOI: https://doi.org/10.1016/j.ijbiomac.2024.137891
[31] M. I. Saidin, I. M. Isa, M. S. Rosmi, N. Hashim, M. S. Ahmad, S. N. A. Mohd Yazid, A. A. Bahari, High-sensitivity electrochemical sensor for paraquat monitoring. International Journal of Environmental Analytical Chemistry 105 (2025) 3919-3933. https://dx.doi.org/10.1080/03067319.2024.2356032 DOI: https://doi.org/10.1080/03067319.2024.2356032
[32] N. Broli, M. Vasjari, L. Vallja, S. Duka, A. Shehu, S. Cenolli, Electrochemical determination of atenolol and propranolol, Open Chemistry 19 (2021) 875-883. https://dx.doi.org/10.1515/chem-2021-0071 DOI: https://doi.org/10.1515/chem-2021-0071
[33] E. Hoxha, N. Broli, M. Vasjari, Multiwalled carbon nanotube-CPE modified electrode, Journal of Natural Sciences 36 (2024) 64-76. https://dx.doi.org/10.70827/1224mcncme DOI: https://doi.org/10.70827/1224mcncme
[34] S. Yu, X. Sun, Z. Yu, J. Jung, S. Ishii, C. T. Hayes, V. C. Pierre, A. H. Flood, J. D. Azoulay, T. N. Ng, Flexible point-of-use phosphate electrochemical sensors, Materials Horizons 12 (2025) 6784-6792. https://dx.doi.org/10.1039/D5MH00692A DOI: https://doi.org/10.1039/D5MH00692A
[35] S. Wei, D. Xiao, C. Bian, Y. Li, Phosphate and nitrate electrochemical sensor based on boron-doped diamond electrode, ACS Omega 9 (2024) 20293-20303. https://dx.doi.org/10.1021/acsomega.4c00717 DOI: https://doi.org/10.1021/acsomega.4c00717
[36] J. Jońca, V. León Fernández, D. Thouron, A. Paulmier, M. Graco, V. Garçon. Phosphate determination in seawater, Talanta 87 (2011) 161-167. https://dx.doi.org/10.1016/j.talanta.2011.09.056 DOI: https://doi.org/10.1016/j.talanta.2011.09.056
[37] Y. He, C. Han, H. Du, Y. Ye, C. Tao, Potentiometric phosphate ion sensor using copper electrode, Chemosensors 12 (2024) 53. https://dx.doi.org/10.3390/chemosensors12040053 DOI: https://doi.org/10.3390/chemosensors12040053
[38] F. G. Hong, L. T. Gao. Electrochemical detection of phosphate in agricultural fertilizers. International Journal of The Electrochemical Science 20 (2025) 101147. https://dx.doi.org/10.1016/j.ijoes.2025.101147 DOI: https://doi.org/10.1016/j.ijoes.2025.101147
[39] M. J. Basumatary, D. Kalita, R. L. Sarma, J. Rajbongshi. Ferrioxalate complex derived electrochemical sensor, Asian Journal of Chemistry 37 (2025) 3019-3024. https://dx.doi.org/10.14233/ajchem.2025.34647 DOI: https://doi.org/10.14233/ajchem.2025.34647
[40] K. Xu, J. Xing, M. Mei, J. Wu, X. Huang, X. Zhang, Y. Liu, Y. Wu, Y. Zhang, F. Ren, X. Li, Electrochemical sensor for phosphate detection using cobalt-nickel alloy, Microchemical Journal 217 (2025) 114928. https://dx.doi.org/10.1016/j.microc.2025.114928 DOI: https://doi.org/10.1016/j.microc.2025.114928
[41] D. A. Skoog, F. J. Holler, S. R. Crouch. Principles of Instrumental Analysis. Cengage Learning, USA, 2019. ISBN-13: 978-1305577213
[42] J. Wang. Analytical Electrochemistry, 3rd ed., Wiley, USA, 2006. ISBN-13: 978-0471678793
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