Effect of Voltage Variation on the Synthesis and Properties of Electrochemically Exfoliated Graphene from Dry-Cell Battery Waste for Chromium Ions Adsorption

https://doi.org/10.22146/ijc.109307

Nenden Fauziah(1*), Rini Febi Nuraeni(2), Fitri Dara(3), Rafiq Arsyad(4), Nadiatus Silmi(5), Veinardi Suendo(6)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Garut, Jl. Prof. Aam Hamdani No. 42, Garut 44151, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Garut, Jl. Prof. Aam Hamdani No. 42, Garut 44151, Indonesia
(3) Research Center for Environmental and Clean Technologies, National Research and Innovation Agency, KST Samaun Samadikun, Jl. Sangkuriang, Bandung 40135, Indonesia
(4) Division of Environmental Materials Science, Graduate School of Environmental Science, Hokkaido University, N10W5 Sapporo 060-0810, Japan; Institute for Catalysis, Hokkaido University, Kita, Kita-ku, N21W10 Sapporo 001-0021, Japan
(5) Research Center for Environmental and Clean Technologies, National Research and Innovation Agency, KST Samaun Samadikun, Jl. Sangkuriang, Bandung 40135, Indonesia
(6) Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia; Research Center for Nanosciences and Nanotechnology, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia
(*) Corresponding Author

Abstract


Electrochemical synthesis can produce graphene-like materials containing structural defects, known as electrochemically exfoliated graphene (EEG), due to the presence of oxygen functional groups. These defects provide active sites for the adsorption of chromium ions. This study aims to determine the effect of voltage variation on the electrochemical exfoliation of graphite, specifically to identify the optimal voltage for producing EEG materials with the highest chromium adsorption capacity. We exfoliated graphite rods from dry-cell waste in a 0.2 M sulfuric acid solution at 5, 10, 15, and 20 V. The EEG was characterized with FTIR and Raman spectroscopy. The adsorption capacity was measured by AAS using 0.1 g of adsorbent in 10 mL of a 50 ppm Cr(VI) solution at pH 2 for 1 h. FTIR confirmed samples are reduced graphene oxide, showing hydroxyl, epoxy, carbonyl, carboxyl, and sulfonate groups. Raman spectroscopy revealed that EEG_15V was the most graphene-like, with the highest I2D/ID ratio. EEG_15V had the greatest Cr(VI) adsorption capacity at 5.27 mg/g.


Keywords


electrochemical exfoliation; graphene oxide (GO); adsorption; chromium (VI); battery waste



References

[1] Xie, S., 2024, Water contamination due to hexavalent chromium and its health impacts: Exploring green technology for Cr (VI) remediation, Green Chem. Lett. Rev., 17 (1), 2356614.

[2] Mohanty, S., Benya, A., Hota, S., Kumar, M.S., and Singh, S., 2023, Eco-toxicity of hexavalent chromium and its adverse impact on environment and human health in Sukinda Valley of India: A review on pollution and prevention strategies, Environ. Chem. Ecotoxicol., 5, 46–54.

[3] Krawic, C., and Zhitkovich, A., 2023, Chemical mechanisms of DNA damage by carcinogenic chromium(VI), Adv. Pharmacol., 96, 25–46.

[4] Widyantoro, A., Maziya, F.B., and Abidin, A.U., 2021, Exposure analysis of lead (Pb) and chromium (Cr) in workplace workshop PT. X, Gac. Sanit., 35, S450–S454.

[5] Rahman, Z., and Singh, V.P., 2019, The relative impact of toxic heavy metals (THMs) (arsenic (As), cadmium (Cd), chromium (Cr)(VI), mercury (Hg), and lead (Pb)) on the total environment: An overview, Environ. Monit. Assess., 191 (7), 419.

[6] Usman, K., Al Jabri, H., Abu-Dieyeh, M.H., and Alsafran, M.H.S.A., 2020, Comparative assessment of toxic metals bioaccumulation and the mechanisms of chromium (Cr) tolerance and uptake in Calotropis procera, Front. Plant Sci., 11, 883.

[7] Freitas, E.C., and Rocha, O., 2014, Acute and chronic toxicity of chromium and cadmium to the tropical cladoceran Pseudosida ramosa and the implications for ecotoxicological studies, Environ. Toxicol., 29 (2), 176–186.

[8] Owlad, M., Aroua, M.K., Wan Daud, W.A., and Baroutian, S., 2009, Removal of hexavalent chromium-contaminated water and wastewater: A review, Water, Air, Soil Pollut., 200 (1), 59–77.

[9] Babel, S., and Kurniawan, T.A., 2003, Low-cost adsorbents for heavy metals uptake from contaminated water: A review, J. Hazard. Mater., 97 (1-3), 219–243.

[10] Saha, B., and Orvig, C., 2010, Biosorbents for hexavalent chromium elimination from industrial and municipal effluents, Coord. Chem. Rev., 254 (23-24), 2959–2972.

[11] Wang, Y., Peng, C., Padilla-Ortega, E., Robledo-Cabrera, A., and López-Valdivieso, A., 2020, Cr(VI) adsorption on activated carbon: Mechanisms, modeling and limitations in water treatment, J. Environ. Chem. Eng., 8 (4), 104031.

[12] Mallik, A.K., Moktadir, M.A., Rahman, M.A., Shahruzzaman, M., and Rahman, M.M., 2022, Progress in surface-modified silicas for Cr(VI) adsorption: A review, J. Hazard. Mater., 423, 127041.

[13] Neolaka, Y.A.B., Lawa, Y., Naat, J., Riwu, A.A.P., Mango, A.W., Darmokoesoemo, H., Widyaningrum, B.A., Iqbal, M., and Kusuma, H.S., 2022, Efficiency of activated natural zeolite-based magnetic composite (ANZ-Fe3O4) as a novel adsorbent for removal of Cr(VI) from wastewater, J. Mater. Res. Technol., 18, 2896–2909.

[14] Rathnayake, S.I., Martens, W.N., Xi, Y., Frost, R.L., and Ayoko, G.A., 2017, Remediation of Cr (VI) by inorganic-organic clay, J. Colloid Interface Sci., 490, 163–173.

[15] Shekhawat, A., Kahu, S., Saravanan, D., Pandey, S., and Jugade, R., 2022, Rational modification of chitosan biopolymer for remediation of Cr(VI) from water, J. Hazard. Mater. Adv., 7, 100123.

[16] Khalajiolyaie, A., and Jian, C., 2025, Advances in graphene-based materials for metal ion sensing and wastewater treatment: A review, Environments, 12 (2), 43.

[17] Li, G., Du, R., Cao, Z., Li, C., Xue, J., Ma, X., and Wang, S., 2024, Research progress in graphene-based adsorbents for wastewater treatment: Preparation, adsorption properties and mechanisms for inorganic and organic pollutants, C, 10 (3), 78.

[18] Huang, J., Cui, W., Liang, R., Zhang, L., and Qiu, J., 2021, Porous BMTTPA-CS-GO nanocomposite for the efficient removal of heavy metal ions from aqueous solutions, RSC Adv., 11 (6), 3725–3731.

[19] Smith, A.T., LaChance, A.M., Zeng, S., Liu, B., and Sun, L., 2019, Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites, Nano Mater. Sci., 1 (1), 31–47.

[20] Melchor-Durán, A.P., Moreno-Virgen, M.R., Bonilla-Petriciolet, A., Reynel-Ávila, H.E., Lucio Ortiz, E., and González-Vázquez, O.F., 2024, Heavy metal removal from water using graphene oxide in magnetic-assisted adsorption systems: Characterization, adsorption properties, and modelling, Separations, 11 (10), 294.

[21] Jawad, N.A., and Naife, T.M., 2023, Removal of heavy metal ions from aqueous solution by nano graphene oxide, Chem. Chem. Technol., 17 (4), 894–902.

[22] Philip, R.S., Aparna, N., and Mathew, M., 2024, Hexavalent chromium removal using reduced graphene oxide-zinc oxide composite fabricated via simple pyrolysis method, Appl. Surf. Sci. Adv., 19, 100535.

[23] Gonçalves, M.G., Costa, V.O., Martinez, A.H.G., Régnier, B.M., Gomes, G.C.B., Zarbin, A.J.G., and Orth, E.S., 2024, Functionalization of graphene oxide via epoxide groups: A comprehensive review of synthetic routes and challenges, Front. Carbon, 3, 1393077.

[24] Lach, J., and Okoniewska, E., 2023, Adsorption of chromium and nickel ions on commercial activated carbon—An analysis of adsorption kinetics and statics, Molecules, 28 (21), 7413.

[25] Gao, C., Dong, Z., Hao, X., Yao, Y., and Guo, S., 2020, Preparation of reduced graphene oxide aerogel and its adsorption for Pb(II), ACS Omega, 5 (17), 9903–9911.

[26] Alija, A., Gashi, D., Plakaj, R., Omaj, A., Thaçi, V., Reka, A., Avdiaj, S., and Berisha, A., 2020, A theoretical and experimental study of the adsorptive removal of hexavalent chromium ions using graphene oxide as an adsorbent, Open Chem., 18 (1), 936–942.

[27] Khdoor, Z., Makharza, S., Qurie, M., Fohely, F., Abu Taha, A., and Hampel, S., 2024, Removal of toxic hexavalent chromium via graphene oxide nanoparticles: Study of kinetics, isotherms, and thermodynamics, RSC Adv., 14 (34), 24345–24351.

[28] Mondal, N.K., and Chakraborty, S., 2020, Adsorption of Cr(VI) from aqueous solution on graphene oxide (GO) prepared from graphite: Equilibrium, kinetic and thermodynamic studies, Appl. Water Sci., 10 (2), 61.

[29] Sunarya, R.R., Hidayat, R., Radiman, C.L., and Suendo, V., 2020, Electrocatalytic activation of a DSSC graphite composite counter electrode using in situ polymerization of aniline in a water/ethanol dispersion of reduced graphene oxide, J. Electron. Mater., 49 (5), 3182–3190.

[30] Guerrero-Contreras, J., and Caballero-Briones, F., 2015, Graphene oxide powders with different oxidation degree, prepared by synthesis variations of the Hummers method, Mater. Chem. Phys., 153, 209–220.

[31] Fatya, A.I., Reza, M., Sunarya, R.R., and Suendo, V., 2020, Synthesis of polyaniline/electrochemically exfoliated graphene composite as counter-electrode in dye-sensitized solar cell, Polym.-Plast. Technol. Mater., 59 (12), 1370–1378.

[32] Parvez, K., Li, R., Puniredd, S.R., Hernandez, Y., Hinkel, F., Wang, S., Feng, X., and Müllen, K., 2013, Electrochemically exfoliated graphene as solution-processable, highly conductive electrodes for organic electronics, ACS Nano, 7 (4), 3598–3606.

[33] Salverda, M., Thiruppathi, A.R., Pakravan, F., Wood, P.C., and Chen, A., 2022, Electrochemical exfoliation of graphite to graphene-based nanomaterials, Molecules, 27 (24), 8643.

[34] Fauziah, N., Silmi, N., Nugroho, F.G., Putra, K.L.H., Benu, D.P., Steky, F.V., Sunarya, R.R., Yuliarto, B., Hidayat, R., and Suendo, V., 2023, Ultrasonication-modified electrochemically exfoliated graphene for counter electrode in dye-sensitized solar cells, Carbon Trends, 12, 100292.

[35] Tuzemen, G.B., 2024, Production of graphene by electrochemical exfoliation method and energy applications, International Conference on Engineering, Natural Sciences, and Technological Developments (ICENSTED 2024), July 19–21, 2024.

[36] Ambrosi, A., and Pumera, M., 2016, Electrochemically exfoliated graphene and graphene oxide for energy storage and electrochemistry applications, Chem. - Eur. J., 22 (1), 153–159.

[37] Marković, Z.M., Budimir, M.D., Kepić, D.P., Holclajtner-Antunović, I.D., Marinović-Cincović, M.T., Dramićanin, M.D., Spasojević, V.D., Peruško, D.B., Špitalský, Z., Mičušik, M., Pavlović, V.B., and Todorović-Marković, B.M., 2016, Semi-transparent, conductive thin films of electrochemical exfoliated graphene, RSC Adv., 6 (45), 39275–39283.

[38] Ali, M.E.A., 2019, Preparation of graphene nanosheets by electrochemical exfoliation of a graphite-nanoclay composite electrode: Application for the adsorption of organic dyes, Colloids Surf., A, 570, 107–116.

[39] He, D., Marsden, A.J., Li, Z., Zhao, R., Xue, W., and Bissett, M.A., 2019, A single step strategy to fabricate graphene fibres via electrochemical exfoliation for micro-supercapacitor applications, Electrochim. Acta, 299, 645–653.

[40] Edison, T.N.J.I., Atchudan, R., Karthik, N., Chandrasekaran, P., Perumal, S., Arunachalam, P., Raja, P.B., Sethuraman, M.G., and Lee, Y.R., 2021, Electrochemically exfoliated graphene sheets as electrode material for aqueous symmetric supercapacitors, Surf. Coat. Technol., 416, 127150.

[41] Zhao, X., Li, H., Han, F., Dai, M., Sun, Y., Song, Z., Han, D., and Niu, L., 2020, Electrochemical exfoliation of graphene as an anode material for ultra-long cycle lithium ion batteries, J. Phys. Chem. Solids, 139, 109301.

[42] Alhajji, E., Zhang, F., and Alshareef, H.N., 2021, Status and prospects of laser-induced graphene for battery applications, Energy Technol., 9 (10), 2100454.

[43] Masemola, D.P., Mafa, P.J., Nyoni, H., Mamba, B.B., and Msagati, T.A.M., 2020, Gold nanoparticles modified exfoliated graphite electrode as electrochemical sensor in the determination of psychoactive drug, J. Environ. Sci. Health, Part B, 55 (5), 455–461.

[44] Han, J., Zhang, Y., Mei, J., Qiu, Z., Pan, K., Jiang, J., Zheng, F., Huang, Y., Wang, H., and Li, Q., 2024, Superior instant heating and electrothermal performances of interconnected graphene-expanded graphite-based electric heating composite, ACS Appl. Nano Mater., 7 (11), 12579–12591.

[45] Chen, J., Perez-Page, M., Ji, Z., Zhang, Z., Guo, Z., and Holmes, S., 2021, One step electrochemical exfoliation of natural graphite flakes into graphene oxide for polybenzimidazole composite membranes giving enhanced performance in high temperature fuel cells, J. Power Sources, 491, 229550.

[46] Rout, D.R., and Jena, H.M., 2023, Synthesis of graphene oxide-modified porous chitosan cross-linked polyaniline composite for static and dynamic removal of Cr(VI), Environ. Sci. Pollut. Res., 30 (9), 22992–23011.

[47] Neolaka, Y.A.B., Lawa, Y., Naat, J.N., Riwu, A.A.P., Iqbal, M., Darmokoesoemo, H., and Kusuma, H.S., 2020, The adsorption of Cr(VI) from water samples using graphene oxide-magnetic (GO-Fe3O4) synthesized from natural cellulose-based graphite (kusambi wood or Schleichera oleosa): Study of kinetics, isotherms and thermodynamics, J. Mater. Res. Technol., 9 (3), 6544–6556.

[48] Kaushal, A., and Singh, S.K., 2017, Critical analysis of adsorption data statistically, Appl. Water Sci., 7 (6), 3191–3196.

[49] Gul, W., and Alrobei, H., 2021, Effect of graphene oxide nanoparticles on the physical and mechanical properties of medium density fiberboard, Polymers, 13 (11), 1818.

[50] Nandiyanto, A.B.D., Oktiani, R., and Ragadhita, R., 2019, How to read and interpret FTIR spectroscope of organic material, Indones. J. Sci. Technol., 4 (1), 97–118.

[51] Claramunt, S., Varea, A., López-Díaz, D., Velázquez, M.M., Cornet, A., and Cirera, A., 2015, The importance of interbands on the interpretation of the Raman spectrum of graphene oxide, J. Phys. Chem. C, 119 (18), 10123–10129.

[52] King, A.A.K., Davies, B.R., Noorbehesht, N., Newman, P., Church, T.L., Harris, A.T., Razal, J.M., and Minett, A.I., 2016, A new Raman metric for the characterisation of graphene oxide and its derivatives, Sci. Rep., 6 (1), 19491.

[53] López-Díaz, D., Delgado-Notario, J.A., Clericò, V., Diez, E., Merchán, M.D., and Velázquez, M.M., 2020, Towards understanding the Raman spectrum of graphene oxide: The effect of the chemical composition, Coatings, 10 (6), 524.

[54] Hao, Y., Wang, Y., Wang, L., Ni, Z., Wang, Z., Wang, R., Koo, C.K., Shen, Z., and Thong, J.T.L., 2010, Probing layer number and stacking order of few-layer graphene by Raman spectroscopy, Small, 6 (2), 195–200.

[55] Ferrari, A.C., and Robertson, J., 2000, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B, 61 (20), 14095–14107.

[56] Abid, A., Sehrawat, P., Islam, S.S., Mishra, P., and Ahmad, S., 2018, Reduced graphene oxide (rGO) based wideband optical sensor and the role of temperature, defect states and quantum efficiency, Sci. Rep., 8 (1), 3537.

[57] Cançado, L.G., Jorio, A., Ferreira, E.H.M., Stavale, F., Achete, C.A., Capaz, R.B., Moutinho, M.V.O., Lombardo, A., Kulmala, T.S., and Ferrari, A.C., 2011, Quantifying defects in graphene via Raman spectroscopy at different excitation energies, Nano Lett., 11 (8), 3190–3196.

[58] Hidayah, N.M.S., Liu, W.W., Lai, C.W., Noriman, N.Z., Khe, C.S., Hashim, U., and Lee, H.C., 2017, Comparison on graphite, graphene oxide and reduced graphene oxide: Synthesis and characterization, AIP Conf. Proc., 1892 (1), 150002.

[59] Adetayo, A., and Runsewe, D., 2019, Synthesis and fabrication of graphene and graphene oxide: A review, Open J. Compos. Mater., 9 (2), 207–229.

[60] Eckmann, A., Felten, A., Mishchenko, A., Britnell, L., Krupke, R., Novoselov, K.S., and Casiraghi, C., 2012, Probing the nature of defects in graphene by Raman spectroscopy, Nano Lett., 12 (8), 3925–3930.

[61] Ferrari, A.C., 2007, Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects, Solid State Commun., 143 (1-2), 47–57.

[62] De Silva, K.K.H., Viswanath, P., Rao, V.K., Suzuki, S., and Yoshimura, M., 2021, New insight into the characterization of graphene oxide and reduced graphene oxide monolayer flakes on Si-based substrates by optical microscopy and Raman spectroscopy, J. Phys. Chem. C, 125 (14), 7791–7798.

[63] Dong, L., Yang, J., Chhowalla, M., and Loh, K.P., 2017, Synthesis and reduction of large sized graphene oxide sheets, Chem. Soc. Rev., 46 (23), 7306–7316.

[64] Ferrari, A.C., and Basko, D.M., 2013, Raman spectroscopy as a versatile tool for studying the properties of graphene, Nat. Nanotechnol., 8 (4), 235–246.

[65] Malard, L.M., Pimenta, M.A., Dresselhaus, G., and Dresselhaus, M.S., 2009, Raman spectroscopy in graphene, Phys. Rep., 473 (5-6), 51–87.

[66] Robertson, J., 2002, Diamond-like amorphous carbon, Mater. Sci. Eng. R Rep., 37 (4-6), 129–281.

[67] Kaushal, A., Dhawan, S.K., and Singh, V., 2019, Determination of crystallite size, number of graphene layers and defect density of graphene oxide (GO) and reduced graphene oxide (RGO), AIP Conf. Proc., 2115 (1), 030106.

[68] You, Y., Deng, J., Tan, X., Gorjizadeh, N., Yoshimura, M., Smith, S.C., Sahajwalla, V., and Joshi, R.K., 2017, On the mechanism of gas adsorption for pristine, defective and functionalized graphene, Phys. Chem. Chem. Phys., 19 (8), 6051–6056.

[69] Li, T., and Yarmoff, J.A., 2018, Defect-induced oxygen adsorption on graphene films, Surf. Sci., 675, 70–77.

[70] Lee, E., and Persson, K.A., 2012, Li absorption and intercalation in single layer graphene and few layer graphene by first principles, Nano Lett., 12 (9), 4624–4628.

[71] Barabanova, L., and Buldum, A., 2024, A first principles study of lithium adsorption in nanoporous graphene, Nanomaterials, 14 (18), 1528.



DOI: https://doi.org/10.22146/ijc.109307

Article Metrics

Abstract views : 202 | views : 47 | views : 21


Copyright (c) 2026 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

 

Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Web Analytics View The Statistics of Indones. J. Chem.