Synergistic Ni-Co interaction and phase control in bimetallic catalyst for ethanol electrooxidation reaction

Original scientific paper

Authors

  • Muhammad Fathar Aulia The Center for Science Innovation, Arva Building, Jl. RP. Soeroso, Jakarta Pusat 10350, Indonesia https://orcid.org/0009-0007-9619-109X
  • Abdul Asywalul Fazri Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Negeri Jakarta, Jl. Rawamangun Muka, Jakarta 13220, Indonesia https://orcid.org/0009-0007-2760-2713
  • Suci Winarsih Research Center for Quantum Physics, National Research and Innovation Agency (BRIN), South Tangerang 15314, Indonesia https://orcid.org/0000-0001-8457-7410
  • Mohammad Hamzah Fauzi Research Center for Quantum Physics, National Research and Innovation Agency (BRIN), South Tangerang 15314, Indonesia https://orcid.org/0009-0001-9543-7082
  • Jumaeda Jatmika Research Center for Quantum Physics, National Research and Innovation Agency (BRIN), South Tangerang 15314, Indonesia https://orcid.org/0000-0003-3549-9764
  • Setia Budi Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Negeri Jakarta, Jl. Rawamangun Muka, Jakarta 13220, Indonesia https://orcid.org/0000-0003-1818-949X

DOI:

https://doi.org/10.5599/jese.2875

Keywords:

Ni-Co electrocatalysts, electrodeposition, thin films, phase transition, direct alcohol fuel cells

Abstract

In this study, bimetallic nickel-cobalt electrocatalysts with different Ni:Co ratios were elec­tro­deposited onto indium tin oxide substrates coated by polyethylene terephthalate and evaluated as cost-effective catalysts for ethanol electrooxidation reaction. The physical fea­tures of the catalysts were studied using X-ray diffraction (XRD), Raman spectroscopy and field-emission scanning electron microscopy, along with energy-dispersive X-ray spec­tro­scopy. XRD analysis revealed a phase transition from a mixed face-cantered cubic (FCC) and hexagonal close-packed structure to a single FCC phase, as the cobalt content decre­ased. This change in phases greatly affected the shape of the catalyst, changing from a peb­bly texture in the mixed-phase samples to a smooth, rounded shape in the single-phase FCC samples. The electrochemical properties and catalytic performance of ethanol oxidation in alkaline medium were investigated using cyclic voltammetry and electrochemical impe­dan­ce spectro­scopy. The tested electrocatalysts revealed that NiCo B having Ni:Co ratio 82:18 possess the best catalytic activity compared to the other catalysts, reaching a current den­sity of 14.82 mA cm-2 for ethanol electrooxidation reaction and showing great stability. This better performance is due to its improved physical structure, which boosts the inter­action between nickel and cobalt, and lowers resistance to charge transfer. These findings demon­strate the promise of NiCo as an efficient electrocatalyst for ethanol electrooxidation reaction.

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References

[1] B. C. Ong, S. K. Kamarudin, S. Basri, Direct liquid fuel cells, International Journal of Hydrogen Energy 42 (2017) 10142-10157. https://doi.org/10.1016/j.ijhydene.2017.01.117

[2] J. Zhan, M. Cai, C. Zhang, C. Wang, Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media, Electrochimica Acta 154 (2015) 70-76. https://doi.org/10.1016/j.electacta.2014.12.078

[3] E. S. Kazan-Kaya, M. Bayramoğlu, Investigation of ethanol fuel electrooxidation reaction on Ni-CeO2NRs anode electrocatalyst in alkaline media, Journal of Electroanalytical Chemistry 927 (2022) 116982. https://doi.org/10.1016/J.JELECHEM.2022.116982

[4] B. Braunchweig, D. Hibbitts, M. Neurock, A. Wieckowski, Electrocatalysis: A direct alcohol fuel cell and surface science perspective, Catalysis Today 202 (2013) 197-209. https://doi.org/10.1016/j.cattod.2012.08.013

[5] R. M. Castagna, J. M. Sieben, A. E. Alvarez, M. M. E. Duarte, Electrooxidation of ethanol and glycerol on carbon supported PtCu nanoparticles, International Journal of Hydrogen Energy 44 (2019) 5970-5982. https://doi.org/10.1016/j.ijhydene.2019.01.090

[6] L. S. R. Silva, I. G. Melo, C. T. Meneses, F. E. Lopez-Suarez, K. I. B. Eguiluz, G. R. Salazar-Banda, Effect of temperature on the ethanol electrooxidation at PtNirich@PtrichNi/C catalyst in acidic and alkaline media, Journal of Electroanalytical Chemistry 857 (2020) 1-11. https://doi.org/10.1016/j.jelechem.2019.113754

[7] C. Busó-Rogero, J. Solla-Gullón, F. J. Vidal-Iglesias, E. Herrero, J. M. Feliu, Oxidation of ethanol on platinum nanoparticles: surface structure and aggregation effects in alkaline medium, Journal of Solid State Electrochemistry 20 (2016) 1095-1106. https://doi.org/10.1007/s10008-015-2970-0

[8] W. Yang, H. Wang, F. Fu, PdCu nanoalloys deposited on porous carbon as a highly efficient catalyst for ethanol oxidation, Materials Chemistry and Physics 228 (2019) 175-179. https://doi.org/10.1016/j.matchemphys.2019.02.075

[9] S. Beyhan, K. Uosaki, J. M. Feliu, E. Herrero, Electrochemical and in situ FTIR studies of ethanol adsorption and oxidation on gold single crystal electrodes in alkaline media, Journal of Electroanalytical Chemistry 707 (2013) 89-94. https://doi.org/http://dx.doi.org/10.1016/j.jelechem.2013.08.034

[10] T. V. M. Sreekanth, K. Yoo, J. Kim, Thorn-shaped NiCo2O4 nanoparticles as multi-functional electrocatalysts for electrochemical applications, Journal of the Taiwan Institute of Chemical Engineers 114 (2020) 291-299. https://doi.org/10.1016/j.jtice.2020.09.006

[11] S. Gamal, D. A. Kospa, A. A. Ibrahim, A. I. Ahmed, A. M. A. Ouf, A comparative study of α-Ni(OH)2 and Ni nanoparticle supported ZIF-8@reduced graphene oxide-derived nitrogen doped carbon for electrocatalytic ethanol oxidation, RSC Advances 14 (2024) 5524-5541. https://doi.org/10.1039/d3ra08208c

[12] X. Guo, T. Liang, D. Zhang, M. Zhang, Y. Lin, C. Lai, Facile fabrication of 3D porous nickel networks for electro-oxidation of methanol and ethanol in alkaline medium, Materials Chemistry and Physics 221 (2019) 390-396. https://doi.org/10.1016/j.matchemphys.2018.09.066

[13] I. Danaee, M. Jafarian, F. Forouzandeh, F. Gobal, M. G. Mahjani, Electrocatalytic oxidation of methanol on Ni and NiCu alloy modified glassy carbon electrode, International Journal of Hydrogen Energy 33 (2008) 4367-4376. https://doi.org/10.1016/j.ijhydene.2008.05.075

[14] S. Yu, Y. Zhang, G. Lou, Y. Wu, X. Zhu, H. Chen, Z. Shen, S. Fu, B. Bao, L. Wu, Synthesis of NiMn-LDH Nanosheet@Ni3S2 Nanorod Hybrid Structures for Supercapacitor Electrode Materials with Ultrahigh Specific Capacitance, Scientific Reports 8 (2018) 5246. https://doi.org/10.1038/s41598-018-23642-6

[15] H. Syafei, D.G. Kurniawan, Electrodeposition of CoxNiy Thin Film and Its Catalytic Activity for Ethanol Electrooxidation, Chemistry and Materials 2 (2023) 14-18. https://doi.org/10.56425/cma.v2i1.50

[16] N. A. M. Barakat, F. S. Al-Mubaddel, M. R. Karim, M. Alrashed, H. Y. Kim, Influence of Sn content on the electrocatalytic activity of NiSn alloy nanoparticles-incorporated carbon nanofibers toward methanol oxidation, International Journal of Hydrogen Energy 43 (2018) 21333-21344. https://doi.org/10.1016/J.IJHYDENE.2018.09.196

[17] M. Motlak, N. A. M. Barakat, M. S. Akhtar, A. M. Hamza, B. S. Kim, C. S. Kim, K. A. Khalil, A. A. Almajid, High performance of NiCo nanoparticles-doped carbon nanofibers as counter electrode for dye-sensitized solar cells, Electrochimica Acta 160 (2015) 1-6. https://doi.org/10.1016/j.electacta.2015.02.063

[18] S. Sun, Z. J. Xu, Composition dependence of methanol oxidation activity in nickel-cobalt hydroxides and oxides: An optimization toward highly active electrodes, Electrochimica Acta 165 (2015) 56-66. https://doi.org/10.1016/j.electacta.2015.03.008

[19] S. Budi, R. A. Tawwabin, U. Cahyana, Afriza, M. Paristiowati, Saccharin-assisted galvanostatic electrodeposition of nanocrystalline FeCo films on a flexible substrate, International Journal of Electrochemical Science 15 (2020) 6682-6694. https://doi.org/10.20964/2020.07.74

[20] S. Budi, S. Muhab, A. Soeprapto, B. Kurniawan, A. Manaf, Effect of the electrodeposition potential on the magnetic properties of FeCoNi films, Materials Science-Poland 37 (2019) 389-394. https://doi.org/10.2478/msp-2019-0044

[21] F. Z. Bouzit, A. Nemamcha, H. Moumeni, J. L. Rehspringer, Morphology and Rietveld analysis of nanostructured Co-Ni electrodeposited thin films obtained at different current densities, Surface and Coatings Technology 315 (2017) 172-180. https://doi.org/10.1016/j.surfcoat.2017.02.028

[22] M. Asgari, M. G. Maragheh, R. Davarkhah, E. Lohrasbi, A.N. Golikand, Electrocatalytic oxidation of methanol on the nickel-cobalt modified glassy carbon electrode in alkaline medium, Electrochimica Acta 59 (2012) 284-289. https://doi.org/10.1016/j.electacta.2011.10.091

[23] Chika Shafa Maura, Muhammad Fathar Aulia, Raudhatul Hadawiyah, Wulan Kharisma Dera, Hilman Syafei, Synthesis of CoNi by Electrodeposition Technique and its Application as an Electrocatalyst for Water Splitting, Chemistry and Materials 2 (2023) 72-76. https://doi.org/10.56425/cma.v2i3.64

[24] S. Budi, A. Auliya, S. Winarsih, M. H. Fauzi, N. Yusmaniar, Square-wave pulse electrodeposition of gold nanoparticles for ethanol electrooxidation, Materials Advances 4 (2023) 5556-5563. https://doi.org/10.1039/d3ma00412k

[25] T. M. Huynh, U. Armbruster, C. R. Kreyenschulte, L. H. Nguyen, B. M. Q. Phan, D. A. Nguyen, A. Martin, Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO, Catalysts 6 (2016) 176. https://doi.org/10.3390/catal6110176

[26] M. Y. Rafique, L. Pan, W. S. Khan, M. Z. Iqbal, H. Qiu, M. H. Farooq, M. Ellahi, Z. Guo, Controlled synthesis, phase formation, growth mechanism, and magnetic properties of 3-D CoNi alloy microstructures composed of nanorods, CrystEngComm 15 (2013) 5314-5325. https://doi.org/10.1039/c3ce40385h

[27] E. Blanco, A. B. Dongil, N. Escalona, Synergy between ni and co nanoparticles supported on carbon in guaiacol conversion, Nanomaterials 10(11) (2020) 2199. https://doi.org/10.3390/nano10112199

[28] S. Budi, M. Takahashi, M. G. Sutrisno, W. A. Adi, Z. Fairuza, B. Kurniawan, S. Maenosono, A. A. Umar, Phases evolution and photocatalytic activity of Cu2O films electrodeposited from a non-pH-adjusted solution, Royal Society Open Science 10 (2023) 230247. https://doi.org/10.1098/rsos.230247

[29] U. Sarac, M. C. Baykul, Y. Uguz, Differences Observed in the Phase Structure, Grain Size-Shape, and Coercivity Field of Electrochemically Deposited Ni-Co Thin Films with Different Co Contents, Journal of Superconductivity and Novel Magnetism 28 (2015) 3105-3110. https://doi.org/10.1007/s10948-015-3139-x

[30] A. Karimzadeh, M. Aliofkhazraei, F. C. Walsh, A review of electrodeposited Ni-Co alloy and composite coatings: Microstructure, properties and applications, Surface and Coatings Technology 372 (2019) 463-498. https://doi.org/10.1016/j.surfcoat.2019.04.079

[31] L. Kaufman, H. Nesor, Coupled phase diagrams and thermochemical data for transition metal binary systems - II, Calphad 2 (1978) 81-108. https://doi.org/10.1016/0364-5916(78)90006-8

[32] A. Bensouilah, A. Guittoum, M. Hemmous, A. Bouremana, B. Rahal, C. Yavru, R.M. Öksüzoglu, M. Kechouane, Structure, Microstructure and Magnetic Properties of CoxNi1 0 0 − x Powders Synthesized by Hydrothermal Method, Journal of Superconductivity and Novel Magnetism 30 (2017) 2219-2225. https://doi.org/10.1007/s10948-017-4035-3

[33] T. Omori, K. Oikawa, J. Sato, I. Ohnuma, U. R. Kattner, R. Kainuma, K. Ishida, Partition behavior of alloying elements and phase transformation temperatures in Co-Al-W-base quaternary systems, Intermetallics 32 (2013) 274-283. https://doi.org/10.1016/j.intermet.2012.07.033

[34] M. Elrouby, H. M. A. El-Lateef, M. Sadek, Electrodeposited Pt nanorods on a novel flowered-like nanostructured Ni-Co alloy as an electrocatalyst for methanol oxidation, International Journal of Hydrogen Energy 44 (2019) 13820-13834. https://doi.org/10.1016/j.ijhydene.2019.03.261

[35] M. R. Islam, M. Rahaman, M. M. Billah, M. R. Islam, Hydrothermal synthesis of an MoS2/MnO2 nanocomposite: a unique 3D-nanoflower/1D-nanorod structure for high-performance energy storage applications, Materials Advances 5 (2024) 5307-5321. https://doi.org/10.1039/d4ma00065j

[36] R. Zhou, C. jie Han, X. min Wang, Hierarchical MoS2-coated three-dimensional graphene network for enhanced supercapacitor performances, Journal of Power Sources 352 (2017) 99-110. https://doi.org/10.1016/j.jpowsour.2017.03.134

[37] S. Harinath Babu, N. Madhusudhana Rao, S. Kaleemulla, G. Amarendra, C. Krishnamoorthi, Room-temperature ferromagnetic and photoluminescence properties of indium-tin-oxide nanoparticles synthesized by solid-state reaction, Bulletin of Materials Science 40 (2017) 17-23. https://doi.org/10.1007/s12034-016-1352-2

[38] M. S. Vidhya, G. Ravi, R. Yuvakkumar, D. Velauthapillai, M. Thambidurai, C. Dang, B. Saravanakumar, Nickel-cobalt hydroxide: A positive electrode for supercapacitor applications, RSC Advances 10 (2020) 19410-19418. https://doi.org/10.1039/d0ra01890b

[39] A. H. Sofi, M. A. Shah, K. Asokan, Structural, Optical and Electrical Properties of ITO Thin Films, Journal of Electronic Materials 47 (2018) 1344-1352. https://doi.org/10.1007/s11664-017-5915-9

[40] A. A. Serkov, H. V Snelling, S. Heusing, T. M. Amaral, Laser sintering of gravure printed indium tin oxide films on polyethylene terephthalate for flexible electronics, Scientific Reports 9 (2019) 1773. https://doi.org/10.1038/s41598-018-38043-y

[41] A. Karpuz, H. Kockar, M. Alper, The effect of different chemical compositions caused by the variation of deposition potential on properties of Ni-Co films, Applied Surface Science 257 (2011) 3632-3635. https://doi.org/10.1016/j.apsusc.2010.11.092

[42] B. Yin, S. Zhang, Y. Jiao, Y. Liu, F. Qu, X. Wu, Facile synthesis of ultralong MnO2 nanowires as high performance supercapacitor electrodes and photocatalysts with enhanced photocatalytic activities, CrystEngComm 16 (2014) 9999-10005. https://doi.org/10.1039/c4ce01302f

[43] P. D. S. Correa, E. L. Da Silva, R. F. Da Silva, C. Radtke, B. Moreno, E. Chinarro, C. D. F. Malfatti, Effect of decreasing platinum amount in Pt-Sn-Ni alloys supported on carbon as electrocatalysts for ethanol electrooxidation, International Journal of Hydrogen Energy 37 (2012) 9314-9323. https://doi.org/10.1016/j.ijhydene.2012.03.022

[44] R. Du, Q. Zhong, X. Tan, L. Liao, Z. Tang, S. Chen, D. Yan, X. Zhao, F. Zeng, Optimized Electrodeposition of Ni2O3 on Carbon Paper for Enhanced Electrocatalytic Oxidation of Ethanol, ACS Omega 9 (2024) 30404-30414. https://doi.org/10.1021/acsomega.4c01658

[45] B. Xiong, Y. Zhou, Y. Zhao, J. Wang, X. Chen, R. O’Hayre, Z. Shao, The use of nitrogen-doped graphene supporting Pt nanoparticles as a catalyst for methanol electrocatalytic oxidation, Carbon 52 (2013) 181-192. https://doi.org/10.1016/j.carbon.2012.09.019

[46] K. Rahmani, B. Habibi, NiCo alloy nanoparticles electrodeposited on an electrochemically reduced nitrogen-doped graphene oxide/carbon-ceramic electrode: A low cost electrocatalyst towards methanol and ethanol oxidation, RSC Advances 9 (2019) 34050-34064. https://doi.org/10.1039/c9ra06290d

[47] Q. Zhang, T. Chen, R. Jiang, F. Jiang, Comparison of electrocatalytic activity of Pt1-: XPdx/C catalysts for ethanol electro-oxidation in acidic and alkaline media, RSC Advances 10 (2020) 10134-10143. https://doi.org/10.1039/d0ra00483a

[48] Z. Deng, Q. Yi, Y. Zhang, H. Nie, NiCo/C-N/CNT composite catalysts for electro-catalytic oxidation of methanol and ethanol, Journal of Electroanalytical Chemistry 803 (2017) 95-103. https://doi.org/10.1016/j.jelechem.2017.09.025

[49] C. Yu, Z. Yan, L. Zhu, J. Wen, H. Wang, Z. Xu, Enhanced Catalytic Performance of Bimetallic Nickel-Cobalt Loaded Low-Content Au Catalyst Toward Ethanol Electro-Oxidation, Electrocatalysis 7 (2016) 193-200. https://doi.org/10.1007/s12678-016-0303-4

[50] L. Yaqoob, T. Noor, N. Iqbal, A comprehensive and critical review of the recent progress in electrocatalysts for the ethanol oxidation reaction, RSC Advances 11 (2021) 16768-16804. https://doi.org/10.1039/d1ra01841h

[51] Y. Li, Y. Xu, C. Li, W. Zhu, W. Chen, Y. Zhao, R. Liu, L. Wang, ZIF-67-Derived NiCo-Layered Double Hydroxide@Carbon Nanotube Architectures with Hollow Nanocage Structures as Enhanced Electrocatalysts for Ethanol Oxidation Reaction, Molecules 28(3) (2023) 1173. https://doi.org/10.3390/molecules28031173

[52] A. A. Fazri, A. N. Puspita, S. Ningsih, A. Auliya, Electrodeposition of CoNi Bimetallic Catalyst for Ethanol Electrooxidation Application, Chemistry and Materials 2 (2023) 56-60. https://doi.org/10.56425/cma.v2i3.63

[53] H. Syafei, Dwi Giwang Kurniawan, Electrodeposition of CoxNiy Thin Film and Its Catalytic Activity for Ethanol Electrooxidation, Chemistry and Materials 2 (2023) 14-18. https://doi.org/10.56425/cma.v2i1.50

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Published

12-10-2025

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Vol. 16 (2026)

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Fuel cells

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Copyright (c) 2025 Muhammad Fathar Aulia, Abdul Asywalul Fazri, Suci Winarsih, Mohammad Hamzah Fauzi, Jumaeda Jatmika, Setia Budi

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How to Cite

Synergistic Ni-Co interaction and phase control in bimetallic catalyst for ethanol electrooxidation reaction: Original scientific paper. (2025). Journal of Electrochemical Science and Engineering, 16, Article 2875. https://doi.org/10.5599/jese.2875

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