A Review: Modified Graphene-Based Voltammetric Sensors for Heavy Metal Detection in Water Samples
DOI:
https://doi.org/10.24114/ijcst.v9i1.72345Keywords:
graphene, heavy metals, voltammetric sensor, surface modification, voltammetricAbstract
Heavy metal contamination in aquatic environments poses a serious environmental and public health concern, requiring analytical methods that are sensitive, selective, and suitable for on-site analysis. Voltammetric electrochemical sensors have emerged as a promising alternative to conventional techniques due to their low cost, portability, rapid response, and high sensitivity. Graphene, with its high surface area, excellent electrical conductivity, and chemical stability, has been widely utilized as an electrode material to enhance sensor performance. However, pristine graphene often exhibits limited selectivity toward specific metal ions. To address this limitation, various surface modification strategies have been developed, including functionalization with chelating ligands, ion-selective polymers, nanoparticles, and composite materials. This review provides a comprehensive overview of recent advances in modified graphene-based voltammetric sensors for heavy metal detection in water samples, covering voltammetric principles, graphene modification strategies, analytical performance, and practical environmental applications.References
1. Xiang H, Cai Q, Li Y, Zhang Z, Cao L, Li K, Yang H (2020) Sensors Applied for the Detection of Pesticides and Heavy Metals in Freshwaters. J Sensors 2020:1–22
2. Lace A, Cleary J (2021) A Review of Microfluidic Detection Strategies for Heavy Metals in Water. Chemosensors 9:60
3. Dag N, Arici OK (2021) Heavy Metals in Soils Pb (Lead), Hg (Mercury), Cd (Cadmium), As (Arsenic) Effects on Human Health. Int J Environ Trends 5:48–59
4. Sulthana SF, Iqbal UM, Suseela SB, Anbazhagan R, Chinthaginjala R, Chitathuru D, Ahmad I, Kim T (2024) Electrochemical Sensors for Heavy Metal Ion Detection in Aqueous Medium: A Systematic Review. ACS Omega 9:25493–25512
5. Chen Y, He M, Chen B, Hu B (2021) Thiol-grafted magnetic polymer for preconcentration of Cd, Hg, Pb from environmental water followed by inductively coupled plasma mass spectrometry detection. Spectrochim Acta Part B At Spectrosc 177:106071
6. Ahmad H, Koo BH, Khan RA (2022) Enrichment of trace Hg(II) ions from food and water samples after solid phase extraction combined with ICP-OES determination. Microchem J 175:107179
7. Daşbaşı T, Saçmacı Ş, Ülgen A, Kartal Ş (2015) A solid phase extraction procedure for the determination of Cd(II) and Pb(II) ions in food and water samples by flame atomic absorption spectrometry. Food Chem 174:591–596
8. Kassim NSA, A. I. S. M. Ghazali S, Liyana Bohari F, A. Z. Abidin N (2022) Assessment of heavy metals in wastewater plant effluent and lake water by using atomic absorption spectrophotometry. Mater Today Proc 66:3961–3964
9. Zhou S, Yuan Z, Cheng Q, Zhang Z, Yang J (2018) Rapid in situ determination of heavy metal concentrations in polluted water via portable XRF: Using Cu and Pb as example. Environ Pollut 243:1325–1333
10. Tighe M, Bielski M, Wilson M, Ruscio-Atkinson G, Peaslee GF, Lieberman M (2020) A Sensitive XRF Screening Method for Lead in Drinking Water. Anal Chem 92:4949–4953
11. Shi Y, Zhang S, Zhou H, Dong Y, Liu G, Ye W, He R, Zhao G (2025) Recent Developments in Heavy Metals Detection: Modified Electrodes, Pretreatment Methods, Prediction Models and Algorithms. Metals (Basel) 15:80
12. Dai X, Wu S, Li S (2018) Progress on electrochemical sensors for the determination of heavy metal ions from contaminated water. J Chinese Adv Mater Soc 6:91–111
13. Ding R, Cheong YH, Ahamed A, Lisak G (2021) Heavy Metals Detection with Paper-Based Electrochemical Sensors. Anal Chem 93:1880–1888
14. Yang Z (2024) Voltammetry for quantitative determination of trace mercury ions in water via acetylene black modified carbon paste electrode. Alexandria Eng J 87:107–113
15. Joshi RK, Alwarappan S, Yoshimura M, Sahajwalla V, Nishina Y (2015) Graphene oxide: the new membrane material. Appl Mater Today 1:1–12
16. Kartika AE, Setiyanto H, Manurung RV, Jenie SNA, Saraswaty V (2021) Silver Nanoparticles Coupled with Graphene Nanoplatelets Modified Screen-Printed Carbon Electrodes for Rhodamine B Detection in Food Products. ACS Omega 6:31477–31484
17. Ambrosi A, Chua CK, Latiff NM, Loo AH, Wong CHA, Eng AYS, Bonanni A, Pumera M (2016) Graphene and Its Electrochemistry – An Update. Chem Soc Rev 45:2458–2493
18. Urade AR, Lahiri I, Suresh KS (2023) Graphene Properties, Synthesis and Applications: A Review. JOM 75:614–630
19. Abdelshafi NA, Darwish HW, Alanazi AS, Naguib IA, Elkhouly HH, Khodary NS, Mohamed EH (2024) Voltammetric analysis of pholcodine on graphene-modified GNPs/PTs with green assessment. BMC Chem 18:48
20. Sheng Z, Cao M, Hong Y, Wang S, Fan Z, Xiong J, Yang H, Deng C (2018) Preparation of Functionalized Graphene Nano-platelets and Use for Adsorption of Pb2+ from Solution. J Wuhan Univ Technol Sci Ed 33:1395–1401
21. Pushpanjali PA, Manjunatha JG, Hareesha N, Amrutha BM, Raril C, ALOthman ZA, Alanazi AM, Pandith A (2022) Fabrication of poly(ʟ-Aspartic acid) Layer on graphene nanoplatelets paste electrode for riboflavin sensing. Mater Chem Phys 276:125392
22. Beyyavaş E, Aslanoglu M (2025) An Electrochemical Platform Constructed with Tantalum Nanoparticles and Graphene Nanoplatelets for the Voltammetric Sensing of Ritodrine. Electroanalysis. https://doi.org/10.1002/elan.12029
23. Zheng Z, Yang X, Li J, Zhang X, Muhammad I, Geng L (2021) Preparation and properties of graphene nanoplatelets reinforced aluminum composites. Trans Nonferrous Met Soc China 31:878–886
24. Wenzel TJ (2013) Douglas A. Skoog, Donald M. West, F. James Holler, and Stanley R. Crouch: Fundamentals of analytical chemistry, 9th ed., international ed. Anal Bioanal Chem 405:7903–7904
25. Kounaves SP (1997) Voltammetric Techniques. Handb. Instrum. Tech. Anal. Chem.
26. Ensafi AA, Amini M, Heydari-Bafrooei E (2016) Interaction of Codeine with DNA. In: Neuropathol. Drug Addict. Subst. Misuse. Elsevier, pp 490–496
27. Chatziathanasiou E, Liava V, Golia EE, Girousi S (2024) Analytical Applications of Voltammetry in the Determination of Heavy Metals in Soils, Plant Tissues, and Water—Prospects and Limitations in the Co-Identification of Metal Cations in Environmental Samples. Analytica 5:358–383
28. Cadena A, Texier A –C., González I, Cervantes FJ, Gómez J (2007) Qualitative And Quantitative Determination Of A Humic Model Compound In Microbial Cultures By Cyclic Voltammetry. Environ Technol 28:1035–1044
29. Allen J. Bard, Larry R. Faulkner HSW (2022) Electrochemical Methods : Fundamental and Applications, Third Edit. John Wiley & Sons, USA
30. Elgrishi N, Rountree KJ, McCarthy BD, Rountree ES, Eisenhart TT, Dempsey JL (2018) A Practical Beginner’s Guide to Cyclic Voltammetry. J Chem Educ 95:197–206
31. Stojek Z (2010) Pulse Voltammetry. In: Electroanal. Methods. Springer Berlin Heidelberg, Berlin, Heidelberg, pp 107–119
32. Lovrić M (2010) Stripping Voltammetry. In: Electroanal. Methods. Springer Berlin Heidelberg, Berlin, Heidelberg, pp 201–221
33. Douglas A. Skoog, Donald M. West, F. James Holler dan SRC (2013) Fundamentals of Analytical Chemistry. Cengage Learning
34. Gafurov ZN, Kantyukov AO, Kagilev AA, Sinyashin OG, Yakhvarov DG (2021) Electrochemical methods for synthesis and in situ generation of organometallic compounds. Coord Chem Rev 442:213986
35. Alyamni N, Abot JL, Zestos AG (2024) Perspective—Advances in Voltammetric Methods for the Measurement of Biomolecules. ECS Sensors Plus 3:027001
36. Yang Q, Nagar B, Alvarez-Diduk R, et al (2021) Development of a Heavy Metal Sensing Boat for Automatic Analysis in Natural Waters Utilizing Anodic Stripping Voltammetry. ACS ES&T Water 1:2470–2476
37. Bressi V, Chiarotto I, Ferlazzo A, Celesti C, Michenzi C, Len T, Iannazzo D, Neri G, Espro C (2023) Voltammetric Sensor Based on Waste‐Derived Carbon Nanodots for Enhanced Detection of Nitrobenzene. ChemElectroChem. https://doi.org/10.1002/celc.202300004
38. Sengupta P, Pramanik K, Sarkar P (2021) Simultaneous detection of trace Pb(II), Cd(II) and Hg(II) by anodic stripping analyses with glassy carbon electrode modified by solid phase synthesized iron-aluminate nano particles. Sensors Actuators B Chem 329:129052
39. Naseri M, Mohammadniaei M, Ghosh K, et al (2023) A Robust Electrochemical Sensor Based on Butterfly‐shaped Silver Nanostructure for Concurrent Quantification of Heavy Metals in Water Samples. Electroanalysis. https://doi.org/10.1002/elan.202200114
40. Jjagwe J, Olupot PW, Kulabako R, Carrara S (2024) Electrochemical sensors modified with iron oxide nanoparticles/nanocomposites for voltammetric detection of Pb (II) in water: A review. Heliyon 10:e29743
41. Filippidou MK, Chatzandroulis S (2023) Microfluidic Devices for Heavy Metal Ions Detection: A Review. Micromachines. https://doi.org/10.3390/mi14081520
42. Ivanišević I (2023) The Role of Silver Nanoparticles in Electrochemical Sensors for Aquatic Environmental Analysis. Sensors. https://doi.org/10.3390/s23073692
43. Sati A, Ranade TN, Mali SN, Ahmad Yasin HK, Pratap A (2025) Silver Nanoparticles (AgNPs): Comprehensive Insights into Bio/Synthesis, Key Influencing Factors, Multifaceted Applications, and Toxicity─A 2024 Update. ACS Omega 10:7549–7582
44. Malik S, Singh J, Goyat R, Saharan Y, Chaudhry V, Umar A, Ibrahim AA, Akbar S, Ameen S, Baskoutas S (2023) Nanomaterials-based biosensor and their applications: A review. Heliyon 9:e19929
45. Bulemo PM, Kim DH, Shin H, et al (2025) Selectivity in Chemiresistive Gas Sensors: Strategies and Challenges. Chem Rev 125:4111–4183
46. Wang C, Ahmad SF, Bani Ahmad Ayassrah AYA, Awwad EM, Irshad M, Ali YA, Al-Razgan M, Khan Y, Han H (2023) An empirical evaluation of technology acceptance model for Artificial Intelligence in E-commerce. Heliyon 9:e18349
47. Rahman HA, Rafi M, Putra BR, Wahyuni WT (2023) Electrochemical Sensors Based on a Composite of Electrochemically Reduced Graphene Oxide and PEDOT:PSS for Hydrazine Detection. ACS Omega 8:3258–3269
48. Hua Y, Mai J, Su R, Ma C, Liu J, Zhao C, Zhang Q, Liao C, Wang Y (2024) A Highly Stable Electrochemical Sensor Based on a Metal–Organic Framework/Reduced Graphene Oxide Composite for Monitoring the Ammonium in Sweat. Biosensors. https://doi.org/10.3390/bios14120617
49. Imbrogno A, Nguyen MN, Schäfer AI (2024) Tutorial review of error evaluation in experimental water research at the example of membrane filtration. Chemosphere. https://doi.org/10.1016/j.chemosphere.2024.141833
50. Liu N, Ye W, Liu G, Zhao G (2022) Improving the accuracy of stripping voltammetry detection of Cd2+ and Pb2+ in the presence of Cu2+ and Zn2+ by machine learning: Understanding and inhibiting the interactive interference among multiple heavy metals. Anal Chim Acta 1213:339956
51. Das S, Sudhagar P, Kang YS, Choi W (2015) Synthesis and Characterization of Graphene. In: Carbon Nanomater. Adv. Energy Syst. Wiley, pp 85–131
52. Yu W, Sisi L, Haiyan Y, Jie L (2020) Progress in the functional modification of graphene/graphene oxide: a review. RSC Adv 10:15328–15345
53. Geim AK (2009) Graphene: Status and Prospects. Science (80- ) 324:1530–1534
54. Adetayo A, Runsewe D (2019) Synthesis and Fabrication of Graphene and Graphene Oxide: A Review. Open J Compos Mater 09:207–229
55. Tiwari SK, Sahoo S, Wang N, Huczko A (2020) Graphene research and their outputs: Status and prospect. J Sci Adv Mater Devices 5:10–29
56. Mishyn V, Hugo A, Rodrigues T, et al (2022) The holy grail of pyrene-based surface ligands on the sensitivity of graphene-based field effect transistors. Sensors & Diagnostics 1:235–244
57. Gulcin İ, Alwasel SH (2022) Metal Ions, Metal Chelators and Metal Chelating Assay as Antioxidant Method. Processes 10:132
58. Sapari S, Razak NHA, Hasbullah SA, Heng LY, Chong KF, Tan LL (2020) A regenerable screen-printed voltammetric Hg(II) ion sensor based on tris-thiourea organic chelating ligand grafted graphene nanomaterial. J Electroanal Chem 878:114670
59. Verma M, Lee I, Oh J, Kumar V, Kim H (2022) Synthesis of EDTA-functionalized graphene oxide-chitosan nanocomposite for simultaneous removal of inorganic and organic pollutants from complex wastewater. Chemosphere 287:132385
60. Uruş S, Çaylar M, Karteri İ (2016) Synthesis of graphene supported bis (diphenylphosphinomethyl)amino ligands and their Pd(II) and Pt(II) complexes: Highly efficient and recoverable nano-catalysts on vitamin K 3 production. Chem Eng J 306:961–972
61. Pokpas K, Jahed N, Baker PG, Iwuoha EI (2017) Complexation-Based Detection of Nickel(II) at a Graphene-Chelate Probe in the Presence of Cobalt and Zinc by Adsorptive Stripping Voltammetry. Sensors 17:1711
62. Wei P, Zhu Z, Song R, Li Z, Chen C (2019) An ion-imprinted sensor based on chitosan-graphene oxide composite polymer modified glassy carbon electrode for environmental sensing application. Electrochim Acta 317:93–101
63. Raril C, Manjunatha JG (2020) Fabrication of novel polymer-modified graphene-based electrochemical sensor for the determination of mercury and lead ions in water and biological samples. J Anal Sci Technol 11:3
64. Nguyen LD, Doan TCD, Huynh TM, Nguyen VNP, Dinh HH, Dang DMT, Dang CM (2021) An electrochemical sensor based on polyvinyl alcohol/chitosan-thermally reduced graphene composite modified glassy carbon electrode for sensitive voltammetric detection of lead. Sensors Actuators B Chem 345:130443
65. Mahadik M, Patil H, Bodkhe G, Ingle N, Sayyad P, Al-Gahaouri T, Shirsat SM, Shirsat M (2020) EDTA Modified PANI/GO Composite Based Detection of Hg (II) Ions. Front Mater. https://doi.org/10.3389/fmats.2020.00081
66. Beduk T, de Oliveira Filho JI, Ait Lahcen A, Mani V, Salama KN (2021) Inherent Surface Activation of Laser-Scribed Graphene Decorated with Au and Ag Nanoparticles: Simultaneous Electrochemical Behavior toward Uric Acid and Dopamine. Langmuir 37:13890–13902
67. Shi L, Li Y, Rong X, Wang Y, Ding S (2017) Facile fabrication of a novel 3D graphene framework/Bi nanoparticle film for ultrasensitive electrochemical assays of heavy metal ions. Anal Chim Acta 968:21–29
68. Cheng Y, Li H, Fang C, Ai L, Chen J, Su J, Zhang Q, Fu Q (2019) Facile synthesis of reduced graphene oxide/silver nanoparticles composites and their application for detecting heavy metal ions. J Alloys Compd 787:683–693
69. El-Desoky HS, Beltagi AM, Ghoneim MM, El-Hadad AI (2022) The first utilization of graphene nano-sheets and synthesized Fe3O4 nanoparticles as a synergistic electrodeposition platform for simultaneous voltammetric determination of some toxic heavy metal ions in various real environmental water samples. Microchem J 175:106966
70. Nourbakhsh A, Rahimnejad M, Asghary M, Younesi H (2022) Simultaneous electro-determination of trace copper, lead, and cadmium in tap water by using silver nanoparticles and graphene nanoplates as nanocomposite modified graphite electrode. Microchem J 175:107137
71. Lee S, Park S-K, Choi E, Piao Y (2016) Voltammetric determination of trace heavy metals using an electrochemically deposited graphene/bismuth nanocomposite film-modified glassy carbon electrode. J Electroanal Chem 766:120–127
72. Xuan X, Park JY (2018) A miniaturized and flexible cadmium and lead ion detection sensor based on micro-patterned reduced graphene oxide/carbon nanotube/bismuth composite electrodes. Sensors Actuators B Chem 255:1220–1227
73. Pan F, Tong C, Wang Z, Han H, Liu P, Pan D, Zhu R (2021) Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions. Microchim Acta 188:295
74. Zhou J, Pan K, Qu G, Ji W, Ning P, Tang H, Xie R (2022) rGO/MWCNTs-COOH 3D hybrid network as a high-performance electrochemical sensing platform of screen-printed carbon electrodes with an ultra-wide detection range of Cd(II) and Pb(II). Chem Eng J 449:137853
75. Gumpu MB, Veerapandian M, Krishnan UM, Rayappan JBB (2017) Simultaneous electrochemical detection of Cd(II), Pb(II), As(III) and Hg(II) ions using ruthenium(II)-textured graphene oxide nanocomposite. Talanta 162:574–582
76. Jeong S-E, Kim S, Han J-H, Pak JJ (2022) Simple laser-induced graphene fiber electrode fabrication for high-performance heavy-metal sensing. Microchem J 172:106950
77. Mohanadas D, Rohani R, Abdul Rahman SF, Mahmoudi E, Sulaiman Y (2025) Highly Sensitive Titanium-Based MXene-Reduced Graphene Oxide Composite for Efficient Electrochemical Detection of Cadmium and Copper Ions in Water. J Compos Sci 9:1–18
78. Machhindra LA, Yen YK (2022) A Highly Sensitive Electrochemical Sensor for Cd2+ Detection Based on Prussian Blue-PEDOT-Loaded Laser-Scribed Graphene-Modified Glassy Carbon Electrode. Chemosensors. https://doi.org/10.3390/chemosensors10060209
79. Jayaraman N, Palani Y, Jonnalagadda RR, Shanmugam E (2022) Covalently dual functionalized graphene oxide-based multiplex electrochemical sensor for Hg(II) and Cr(VI) detection. Sensors Actuators B Chem 367:132165
80. Wang W-J, Lu X-Y, Kong F-Y, Li H-Y, Wang Z-X, Wang W (2022) A reduced graphene oxide supported Au-Bi bimetallic nanoparticles as an enhanced sensing platform for simultaneous voltammetric determination of Pb (II) and Cd (II). Microchem J 175:107078
81. Hajzus JR, Shriver-Lake LC, Dean SN, Erickson JS, Zabetakis D, Golden J, Pennachio DJ, Myers-Ward RL, Trammell SA (2022) Modifications of Epitaxial Graphene on SiC for the Electrochemical Detection and Identification of Heavy Metal Salts in Seawater. Sensors. https://doi.org/10.3390/s22145367
82. Shan Q, Tian J, Ding Q, Wu W (2022) Electrochemical sensor based on metal-free materials composed of graphene and graphene oxide for sensitive detection of cadmium ions in water. Mater Chem Phys 284:126064












