Bimetal Modified HKUST-1 as Electrode Material for Supercapacitor

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As the demand for energy and technological advancements continues to grow, the need for efficient and high-capacity energy storage devices is also increasing. Supercapacitors have emerged as a potential solution, offering advantages such as high specific capacitance, shorter charging times, and longer lifespan. Metal-Organic Framework (MOF) materials have shown promise potential as various electrodes applications due to their superior surface area and porosity. This study focuses on the development of MOF materials based on HKUST-1 with bimetallic modification at a 1:1 ratio, using cobalt and nickel as the metal center. The synthesis, characterization, and electrochemical testing were conducted to evaluate the potential of each material as an electrode for supercapacitor applications. The synthesis was carried out using the coprecipitation method. SEM and XRD characterizations revealed poor crystallinity, with a morphological change to polyhedral shapes with the addition of Ni and elongated shapes with the addition of Co. Electrochemical tests using cyclic voltammetry and galvanostatic charge discharge techniques demonstrated poor supercapacitor performance, with non-ideal voltammetry curves and relatively low specific capacitance compared to common supercapacitor materials. The trend shows that secondary metals improves the characteristics of HKUST-1 as supercapacitor. It is shown that the HKUST-1 which has been added with Co and Ni is better than regular HKUST-1, with Co being the best out of all three. This trend is also supported by DFT calculations which shows stronger adsorption in Co active sites, followed by Ni and lastly Cu.

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Materials Science Forum (Volume 1177)

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31-39

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February 2026

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© 2026 Trans Tech Publications Ltd. All Rights Reserved

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[1] C. Liu, F. Li, L. Ma, and H. Cheng, "Advanced Materials for Energy Storage," Advanced Materials, vol. 22, no. 8, Feb. 2010.

DOI: 10.1002/adma.200903328

Google Scholar

[2] S. Sharma and P. Chand, "Supercapacitor and electrochemical techniques: A brief review," Results Chem, vol. 5, p.100885, Jan. 2023.

DOI: 10.1016/j.rechem.2023.100885

Google Scholar

[3] F. Bonaccorso et al., "Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage," Science (1979), vol. 347, no. 6217, Jan. 2015.

DOI: 10.1126/science.1246501

Google Scholar

[4] S. P. S. Badwal, S. S. Giddey, C. Munnings, A. I. Bhatt, and A. F. Hollenkamp, "Emerging electrochemical energy conversion and storage technologies," Front Chem, vol. 2, Sep. 2014.

DOI: 10.3389/fchem.2014.00079

Google Scholar

[5] P. Simon and Y. Gogotsi, "Materials for electrochemical capacitors," Nat Mater, vol. 7, no. 11, p.845–854, Nov. 2008.

DOI: 10.1038/nmat2297

Google Scholar

[6] B. E. Conway, Electrochemical Supercapacitors. Boston, MA: Springer US, 1999.

DOI: 10.1007/978-1-4757-3058-6

Google Scholar

[7] S. Shin, J. W. Gittins, C. J. Balhatchet, A. Walsh, and A. C. Forse, "Metal–Organic Framework Supercapacitors: Challenges and Opportunities," Adv Funct Mater, Sep. 2023.

DOI: 10.1002/adfm.202308497

Google Scholar

[8] M. Ko, L. Mendecki, and K. A. Mirica, "Conductive two-dimensional metal–organic frameworks as multifunctional materials," Chemical Communications, vol. 54, no. 57, p.7873–7891, 2018.

DOI: 10.1039/C8CC02871K

Google Scholar

[9] L. Niu et al., "Conductive Metal–Organic Frameworks for Supercapacitors," Advanced Materials, vol. 34, no. 52, Dec. 2022.

DOI: 10.1002/adma.202200999

Google Scholar

[10] H. Zhong, M. Wang, G. Chen, R. Dong, and X. Feng, "Two-Dimensional Conjugated Metal–Organic Frameworks for Electrocatalysis: Opportunities and Challenges," ACS Nano, vol. 16, no. 2, p.1759–1780, Feb. 2022.

DOI: 10.1021/acsnano.1c10544

Google Scholar

[11] K. W. Nam et al., "Conductive 2D metal-organic framework for high-performance cathodes in aqueous rechargeable zinc batteries," Nat Commun, vol. 10, no. 1, p.4948, Oct. 2019.

DOI: 10.1038/s41467-019-12857-4

Google Scholar

[12] D. Sheberla, J. C. Bachman, J. S. Elias, C.-J. Sun, Y. Shao-Horn, and M. Dincă, "Conductive MOF electrodes for stable supercapacitors with high areal capacitance," Nat Mater, vol. 16, no. 2, p.220–224, Feb. 2017.

DOI: 10.1038/nmat4766

Google Scholar

[13] L. Chen, H.-F. Wang, C. Li, and Q. Xu, "Bimetallic metal–organic frameworks and their derivatives," Chem Sci, vol. 11, no. 21, p.5369–5403, 2020.

DOI: 10.1039/D0SC01432J

Google Scholar

[14] S. A. E. Naser, K. O. Badmus, and L. Khotseng, "Synthesis, Properties, and Applications of Metal Organic Frameworks Supported on Graphene Oxide," Coatings, vol. 13, no. 8, p.1456, Aug. 2023.

DOI: 10.3390/coatings13081456

Google Scholar

[15] N. L. Wulan Septiani et al., "Selective synthesis of monodisperse bimetallic nickel–cobalt phosphates with different nanoarchitectures for battery-like supercapacitors," J Mater Chem A Mater, vol. 12, no. 23, p.14045–14058, 2024.

DOI: 10.1039/D3TA06584G

Google Scholar

[16] R. Pech and J. Pickardt, "catena -Triaqua-μ-[1,3,5-benzenetricarboxylato(2–)]-copper(II)," Acta Crystallogr C, vol. 44, no. 6, p.992–994, Jun. 1988.

DOI: 10.1107/S0108270188002902

Google Scholar

[17] L. Zhou, Z. Niu, X. Jin, L. Tang, and L. Zhu, "Effect of Lithium Doping on the Structures and CO 2 Adsorption Properties of Metal‐Organic Frameworks HKUST‐1," ChemistrySelect, vol. 3, no. 45, p.12865–12870, Dec. 2018.

DOI: 10.1002/slct.201803164

Google Scholar

[18] S. Denning, A. A. Majid, J. M. Lucero, J. M. Crawford, M. A. Carreon, and C. A. Koh, "Metal–Organic Framework HKUST-1 Promotes Methane Hydrate Formation for Improved Gas Storage Capacity," ACS Appl Mater Interfaces, vol. 12, no. 47, p.53510–53518, Nov. 2020.

DOI: 10.1021/acsami.0c15675

Google Scholar

[19] M. J. Manos, E. E. Moushi, G. S. Papaefstathiou, and A. J. Tasiopoulos, "New Zn 2+ Metal Organic Frameworks with Unique Network Topologies from the Combination of Trimesic Acid and Amino-Alcohols," Cryst Growth Des, vol. 12, no. 11, p.5471–5480, Nov. 2012.

DOI: 10.1021/cg301047w

Google Scholar

[20] K. K. Dewi et al., "One-Dimensional HKUST-1-Decorated Glassy Carbon Electrode for the Sensitive Electrochemical Immunosensor of NS1 Dengue Virus Serotype-3," ACS Omega, vol. 9, no. 1, p.1454–1462, Jan. 2024.

DOI: 10.1021/acsomega.3c07856

Google Scholar

[21] F. Tian et al., "Synthesis of bimetallic–organic framework Cu/Co-BTC and the improved performance of thiophene adsorption," RSC Adv, vol. 9, no. 27, p.15642–15647, 2019.

DOI: 10.1039/C9RA02372K

Google Scholar

[22] N. Elgrishi, K. J. Rountree, B. D. McCarthy, E. S. Rountree, T. T. Eisenhart, and J. L. Dempsey, "A Practical Beginner's Guide to Cyclic Voltammetry," J Chem Educ, vol. 95, no. 2, p.197–206, Feb. 2018.

DOI: 10.1021/acs.jchemed.7b00361

Google Scholar

[23] X. Hang, J. Zhao, Y. Xue, R. Yang, and H. Pang, "Synergistic effect of Co/Ni bimetallic metal–organic nanostructures for enhanced electrochemical energy storage," J Colloid Interface Sci, vol. 628, p.389–396, Dec. 2022.

DOI: 10.1016/j.jcis.2022.07.136

Google Scholar

[24] Y. Jiao et al., "Mixed-metallic MOF based electrode materials for high performance hybrid supercapacitors," J Mater Chem A Mater, vol. 5, no. 3, p.1094–1102, 2017.

DOI: 10.1039/C6TA09805C

Google Scholar

[25] X. Hu et al., "Hierarchical CuCo2O4@CoS-Cu/Co-MOF core-shell nanoflower derived from copper/cobalt bimetallic metal–organic frameworks for supercapacitors," J Colloid Interface Sci, vol. 600, p.72–82, Oct. 2021.

DOI: 10.1016/j.jcis.2021.05.008

Google Scholar

[26] A. Nuruddin et al., "Oxygen Reduction Reaction Mechanism on the Square Paddle-Wheel Cage Site of TM-BTC (TM=Mn, Fe, Cu) Metal-Organic Framework," Journal of Mathematical and Fundamental Sciences, vol. 54, no. 2, p.233–248, Dec. 2022.

DOI: 10.5614/j.math.fund.sci.2022.54.2.2

Google Scholar

[27] M. K. Agusta, A. G. Saputro, V. V. Tanuwijaya, N. N. Hidayat, and H. K. Dipojono, "Hydrogen Adsorption on Fe-based Metal Organic Frameworks: DFT Study," Procedia Eng, vol. 170, p.136–140, 2017.

DOI: 10.1016/j.proeng.2017.03.030

Google Scholar