NICKEL-INCORPORATED CERIUM METAL ORGANIC FRAMEWORK ON NICKEL FOAM: UNVEILING 3D NANOPILLARS ON 3D SUBSTRATE FOR GREEN HYDROGEN GENERATION VIA WATER SPLITTING
DOI:
https://doi.org/10.3126/jist.v31i1.92566Keywords:
Electrocatalyst, HER, MOFs, Water splittingAbstract
For sustainable hydrogen production through water splitting, the rational engineering of economical and effective electrocatalysts/nanomaterials for the hydrogen evolution reaction (HER) is essential. In this work, we describe the logical design and in-situ development of a nickel-doped cerium metal-organic framework (Ni/Ce-BTC@NF) directly on 3D nickel foam (NF), designing a binder-free (freestanding) electrode with a distinctive three-dimensional (3D) nanopillar-like structure. The unique design of a crystalline Ce-BTC framework with evenly dispersed nickel while maintaining the intrinsic rod-like shape upon doping is confirmed by structural and morphological investigations. Electrochemical measurements reveal that Ni doping significantly enhances HER activity in alkaline medium, with Ni/Ce-BTC@NF achieving overpotentials of 108.9 mV and 196.1 mV to sustain 10 mA cm⁻² and 50 mA cm-2, respectively, outperforming pristine Ce-BTC@NF. Excellent durability is demonstrated by the material’s steady activity throughout a 24-hour time of continuous operation. The Ni/Ce-BTC@NF (−) // RuO2@NF (+) electrolysis configuration exhibits competitive total water-splitting performance requiring 1.67 V (cell voltage) at 10 mA cm-2. This research offers a viable method for designing cerium MOFs-based electrocatalysts with hierarchical topologies and modulated electronic structures for effective hydrogen generation.
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Acharya, D., Chhetri, K., Pathak, I., Muthurasu, A., Mangal Bhattarai, R., Kim, T., Raj Rosyara, Y., Woo Lee, D., Hoon Ko, T., & Yong Kim, H. (2024). Multiphase lattice engineering of bimetallic phosphide-embedded tungsten-based phosphide/oxide nanorods on carbon cloth: A synergistic and stable electrocatalyst for overall water splitting. Chemical Engineering Journal, 499, 155832. https://doi.org/10.1016/j.cej.2024.155832
Acharya, D., Pathak, I., Muthurasu, A., Bhattarai, R. M., Kim, T., Ko, T. H., Saidin, S., Chhetri, K., & Kim, H. Y. (2023). In situ transmogrification of nanoarchitectured Fe-MOFs decorated porous carbon nanofibers into efficient positrode for asymmetric supercapacitor application. Journal of Energy Storage, 63, 106992. https://doi.org/10.1016/j.est.2023.106992
Alkhaldi, R. S., Gondal, M. A., Mohamed, M. J. S., Almessiere, M. A., Baykal, A., Caliskan, S., & Slimani, Y. (2024). Chestnut-like molybdenum-doped nickel cobaltite spinel oxide nanoparticles grown on Ni foam as the electrocatalyst for the hydrogen evolution reaction. ACS Applied Nano Materials, 7(3), 2867—2878. https://doi.org/10.1021/acsanm.3c05156
Amin, B. G., Swesi, A. T., Masud, J., & Nath, M. (2017). CoNi2Se4 as an efficient bifunctional electrocatalyst for overall water splitting. Chemical Communications, 53(39), 5412—5415. https://doi.org/10.1039/c7cc01489a
Amorim, I., Xu, J., Zhang, N., Xiong, D., Thalluri, S. M., Thomas, R., Sousa, J. P. S., Araújo, A., Li, H., & Liu, L. (2020). Bi-metallic cobalt-nickel phosphide nanowires for electrocatalysis of the oxygen and hydrogen evolution reactions. Catalysis Today, 358, 196—202. https://doi.org/10.1016/j.cattod.2019.05.037
Anantharaj, S., Karthick, K., Murugan, P., & Kundu, S. (2020). V3+ Incorporated beta-Co(OH)2: A robust and efficient electrocatalyst for water oxidation. Inorganic Chemistry, 59(1), 730—740. https://doi.org/10.1021/acs.inorgchem.9b02977
Aryal, S., Shrestha, K. R., Shrestha, T., Oli, H. B., Pathak, I., Shrestha, R. L., & Bhattarai, D. P. (2025). Activated carbon from Prunus persica seed stones as a negatrode material for high-performance supercapacitors. Journal of Molecular Structure, 1323, 140810. https://doi.org/10.1016/j.molstruc.2024.140810
Chhetri, K., Acharya, D., Pawale, R. S., Kong, K.-H., Pathak, I., Rosyara, Y. R., Bhattarai, R. M., Lohani, P. C., Kim, T., Kim, N. H., Lee, J. H., Kim, B.-S., Hereijgers, J., Chung, C.-H., Cho, H., Ko, T. H., & Kim, H. Y. (2026). Hemispherical mesoporous hollow carbon nanobowls as a separator-cum-cathode material for enhanced sulfur redox kinetics and polysulfides regulation in Lithium-sulfur batteries. Composites Part B: Engineering, 310, 113159. https://doi.org/10.1016/j.compositesb.2025.113159
Chhetri, K., Muthurasu, A., Dahal, B., Kim, T., Mukhiya, T., Chae, S. H., Ko, T. H., Choi, Y. C., & Kim, H. Y. (2022). Engineering the abundant heterointerfaces of integrated bimetallic sulfide-coupled 2D MOF-derived mesoporous CoS2 nanoarray hybrids for electrocatalytic water splitting. Materials Today Nano, 17, 100146. https://doi.org/10.1016/j.mtnano.2021.100146
Chhetri, K., Pathak, I., Acharya, D., Rosyara, Y. R., Bhattrai, R. M., Kong, K.-H., Kim, B.-S., Kim, T., Ko, T. H., & Kim, H. Y. (2025). Uniquely nanofibrillated hollow carbon nanofibers with decoration of 2D MOF-derived CoMo sulfides: An efficient cathode material for Lithium sulfur batteries. Journal of Energy Storage, 136, 118459. https://doi.org/10.1016/j.est.2025.118459
Dong, T., Zhang, X., Wang, P., Chen, H.-S., & Yang, P. (2020). Formation of Ni-doped MoS2 nanosheets on N-doped carbon nanotubes towards superior hydrogen evolution. Electrochimica Acta, 338, 135885. https://doi.org/10.1016/j.electacta.2020.135885
Dong, T., Zhang, ., Wang, P., Chen, H.-S., & Yang, P. (2020). Formation of Ni-doped MoS2 nanosheets on N-doped carbon nanotubes towards superior hydrogen evolution. Electrochimica Acta, 338. https://doi.org/10.1016/j.electacta.2020.135885
Gu, J. X., Chen, H., Ren, Y., Gu, Z. G., Li, G., Xu, W. J., Yang, X. Y., Wen, J. X., Wu, J. T., & Jin, H. G. (2022). A novel cerium(IV)-based metal-organic framework for CO2 chemical fixation and photocatalytic overall water splitting. ChemSusChem, 15(1), e202102368. https://doi.org/10.1002/cssc.202102368
Gu, J. X., Zhao, P. C., Lin, W., Deng, J., Chao, Z. S., & Jin, H. G. (2024). Cerium(III)‐MOF as a photocatalyst for hydrogen evolution from water splitting. Applied Organometallic Chemistry, 38(9), e7616. https://doi.org/10.1002/aoc.7616
Hu, Z., Wang, Y., & Zhao, D. (2021). The chemistry and applications of hafnium and cerium(iv) metal-organic frameworks. Chemical Society Reviews, 50(7), 4629—4683. https://doi.org/10.1039/d0cs00920b
Jacobsen, J., Ienco, A., D'Amato, R., Costantino, F., & Stock, N. (2020). The chemistry of Ce-based metal-organic frameworks. Dalton Transactions, 49(46), 16551—16586. https://doi.org/10.1039/d0dt02813d
Jamesh, M. I., Kuang, Y., & Sun, X. (2019). Constructing earth‐abundant 3D nanoarrays for efficient overall water splitting – A review. ChemCatChem, 11(6), 1550—1575. https://doi.org/10.1002/cctc.201801783
Janicki, R., Mondry, A., & Starynowicz, P. (2017). Carboxylates of rare earth elements. Coordination Chemistry Reviews, 340, 98-133. https://doi.org/10.1016/j.ccr.2016.12.001
Jin, H. G., Wang, M., Wen, J. X., Han, S. H., Hong, X. J., Cai, Y. P., Li, G., Fan, J., & Chao, Z. S. (2021). Oxygen vacancy-rich mixed-valence cerium MOF: An efficient separator coating to high-performance lithium-sulfur batteries. ACS Applied Materials & Interfaces, 13(3), 3899—3910. https://doi.org/10.1021/acsami.0c18899
Liu, P., Jing, P., Xu, X., Liu, B., & Zhang, J. (2021). Structural reconstruction of Ce-MOF with active sites for efficient electrocatalytic N2 reduction. ACS Applied Energy Materials, 4(11), 12128—12136. https://doi.org/10.1021/acsaem.1c01656
Liu, S., Teng, Z., Liu, H., Wang, T., Wang, G., Xu, Q., Zhang, X., Jiang, M., Wang, C., Huang, W., & Pang, H. (2022). A Ce-UiO-66 metal-organic framework-based graphene-embedded photocatalyst with controllable activation for solar ammonia fertilizer production. Angewandte Chemie International Edition, 61(37), e202207026. https://doi.org/10.1002/anie.202207026
Lu, X. F., Xia, B. Y., Zang, S. Q., & Lou, X. W. D. (2020). Metal-organic frameworks based electrocatalysts for the oxygen reduction reaction. Angewandte Chemie International Edition, 59(12), 4634—4650. https://doi.org/10.1002/anie.201910309
Luo, J., Wang, X., Gu, Y., Wang, S., Li, Y., Wang, T., Liu, Y., Zhou, Y., & Zhang, J. (2023). Hierarchical sheet-like W-doped NiCo2O4 spinel synthesized by high-valence oxyanion exchange strategy for highly efficient electrocatalytic oxygen evolution reaction. Chemical Engineering Journal, 472, 144839. https://doi.org/10.1016/j.cej.2023.144839
Luo, R., Luo, M., Wang, Z., Liu, P., Song, S., Wang, X., & Chen, M. (2019). The atomic origin of nickel-doping-induced catalytic enhancement in MoS2 for electrochemical hydrogen production. Nanoscale, 11(15), 7123—7128. https://doi.org/10.1039/C8NR10023C
Mondal, A., & Vomiero, A. (2022). 2D transition metal dichalcogenides‐based electrocatalysts for hydrogen evolution reaction. Advanced Functional Materials, 32(52). https://doi.org/10.1002/dfm.202208994
Naik Shreyanka, S., Theerthagiri, J., Lee, S. J., Yu, Y., & Choi, M. Y. (2022). Multiscale design of 3D metal–organic frameworks (M−BTC, M: Cu, Co, Ni) via PLAL enabling bifunctional electrocatalysts for robust overall water splitting. Chemical Engineering Journal, 446. https://doi.org/10.1016/j.cej.2022.137045
Pandey, S., Ghimire, M., Kim, T., Jung, M., Asaithambi, S., Dong, W. J., Son, J.-W., Yun, Y. J., & Jun, Y. (2025). Synthesis of porous MXene for efficient bifunctional electrocatalysis in overall water splitting: Hydrogen and oxygen evolution reactions. FlatChem, 50, 100837. https://doi.org/10.1016/j.flatc.2025.100837
Pandey, S., Ghimire, M., Lee, C., Park, J., Olivar Amaya, M. I., Trần, T. T., Son, J.-W., Yun, Y. J., & Jun, Y. (2026). Recent progress on MXene-hematite nanocomposite catalyst for water-splitting applications: Synthesis strategies, synergetic performance, and future perspectives. Fuel, 404, 136248. https://doi.org/10.1016/j.fuel.2025.136248
Pathak, I., Acharya, D., Chhetri, K., Chandra Lohani, P., Hoon Ko, T., Muthurasu, A., Subedi, S., Kim, T., Saidin, S., & Dahal, B. (2023). Ti3C2Tx MXene integrated hollow carbon nanofibers with polypyrrole layers for MOF-derived freestanding electrodes of flexible asymmetric supercapacitors. Chemical Engineering Journal, 469, 143388. https://doi.org/10.1016/j.cej.2023.143388
Pathak, I., Acharya, D., Chhetri, K., Rosyara, Y. R., Kim, T., Ko, T. H., & Kim, H. Y. (2025). Engineering a double-mof-derived Co1–xS/Co9S8 interface modulated by selenium doping and platinum single atoms: an efficient bifunctional electrocatalyst for water splitting. ACS Applied Materials & Interfaces, 17(28), 40443—40456. https://doi.org/10.1021/acsami.5c06979
Pathak, I., Acharya, D., Chhetri, K., Rosyara, Y. R., Muthurasu, A., Kim, T., Ko, T. H., & Kim, H. Y. (2025). Coengineering of Ni-NDC derived graphitic Ni2P/NiSe2 on a Ti3C2Tx MXene-modified 3D self-supporting electrode: Unraveling 2D–2D multiphases for overall water electrolysis. Composites Part B: Engineering, 296, 112238. https://doi.org/10.1016/j.compositesb.2025.112238
Pathak, I., Prabhakaran, S., Acharya, D., Chhetri, K., Muthurasu, A., Rosyara, Y. R., Kim, T., Ko, T. H., Kim, D. H., & Kim, H. Y. (2024). Structural and phase engineering of a hierarchical 2D–2D nickel MOF/hydroxide-derived Ni0.85Se/NiTe2 heterointerface for robust HER, OER, and overall water splitting. Small, 20(52), 2406732. https://doi.org/https://doi.org/10.1002/smll.202406732
Rathore, D., Banerjee, A., & Pande, S. (2022). Bifunctional tungsten-doped Ni(OH)2/NiOOH nanosheets for overall water splitting in an alkaline medium. ACS Applied Nano Materials, 5(2), 2664—2677. https://doi.org/10.1021/acsanm.1c04359
Rosyara, Y. R., Muthurasu, A., Chhetri, K., Pathak, I., Ko, T. H., Lohani, P. C., Acharya, D., Kim, T., Lee, D., & Kim, H. Y. (2024). Highly porous metal–organic framework entrapped by cobalt telluride–manganese telluride as an efficient bifunctional electrocatalyst. ACS Appied Materials & Interfaces, 16(8), 10238. https://pubs.acs.org/doi/10.1021/acsami.3c18654
Rosyara, Y. R., Pathak, I., Muthurasu, A., Acharya, D., Chhetri, K., Kim, T., Poudel, M. B., Ojha, G. P., Ko, T. H., & Kim, H. Y. (2025). Anion-modulated bifunctional electrocatalytic activity of nickel telluride/cobalt telluride mesoporous nanosheets for high-efficiency and stable overall water splitting. Journal of Materials Chemistry A. 13, 41156—41169. https://doi.org/10.1039/D5TA03463A
Senthil Raja, D., Chuah, X. F., & Lu, S. Y. (2018). In situ grown bimetallic MOF‐based composite as highly efficient bifunctional electrocatalyst for overall water splitting with ultrastability at high current densities. Advanced Energy Materials, 8(23), 1801065. https://doi.org/10.1002/aenm.201801065
Senthil Raja, D., Lin, H.-W., & Lu, S.-Y. (2019). Synergistically well-mixed MOFs grown on nickel foam as highly efficient durable bifunctional electrocatalysts for overall water splitting at high current densities. Nano Energy, 57, 1—13. https://doi.org/10.1016/j.nanoen.2018.12.018
Shetty, S., Sadiq, M. M. J., Bhat, D. K., & Hegde, A. C. (2018). Electrodeposition of Ni–Mo–rGO composite electrodes for efficient hydrogen production in an alkaline medium. New Journal of Chemistry, 42(6), 4661—4669. https://doi.org/10.1039/c7nj04552b
Sirati, M. M., Hussain, D., Mahmood, K., Chughtai, A. H., Yousaf-Ur-Rehman, M., Malik, W. M. A., Alomairy, S., Ahmed, S. b., Al-Buriahi, M. S., & Ashiq, M. N. (2022). Single-step hydrothermal synthesis of amine functionalized Ce-MOF for electrochemical water splitting. Journal of Taibah University for Science, 16(1), 525—534. https://doi.org/10.1080/16583655.2022.2079310
Wang, B., Liu, S., Liu, L., Song, W.-W., Zhang, Y., Wang, S.-M., & Han, Z.-B. (2021). MOF/PEDOT/HPMo-based polycomponent hierarchical hollow micro-vesicles for high performance flexible supercapacitors. Journal of Materials Chemistry A, 9(5), 2948—2958. https://doi.org/10.1039/d0ta10603h
Wang, C. P., Lin, Y. X., Cui, L., Zhu, J., & Bu, X. H. (2023). 2D metal-organic frameworks as competent electrocatalysts for water splitting. Small, 19(15), e2207342. https://doi.org/10.1002/smll.202207342
Wang, H., Zhang, X., Yin, F., Chu, W., & Chen, B. (2020). Coordinately unsaturated metal–organic framework as an unpyrolyzed bifunctional electrocatalyst for oxygen reduction and evolution reactions. Journal of Materials Chemistry A, 8(42), 22111—22123. https://doi.org/10.1039/d0ta04331a
Wu, L., Ning, M., Xing, X., Wang, Y., Zhang, F., Gao, G., Song, S., Wang, D., Yuan, C., Yu, L., Bao, J., Chen, S., & Ren, Z. (2023). Boosting oxygen evolution reaction of (Fe,Ni)OOH via defect engineering for anion exchange membrane water electrolysis under industrial conditions. Advanced Materials, 35(44), e2306097. https://doi.org/10.1002/adma.202306097
Wu, X. P., Gagliardi, L., & Truhlar, D. G. (2018). Cerium metal-organic framework for photocatalysis. Journal of American Chemical Society, 140(25), 7904—7912. https://doi.org/10.1021/jacs.8b03613
Xia, H., Zhang, J., Yang, Z., Guo, S., Guo, S., & Xu, Q. (2017). 2D MOF nanoflake-assembled spherical microstructures for enhanced supercapacitor and electrocatalysis performances. Nanomicro Letters, 9(4), 43. https://doi.org/10.1007/s40820-017-0144-6
Xie, L. S., Skorupskii, G., & Dinca, M. (2020). Electrically conductive metal-organic frameworks. Chemical Reviews, 120(16), 8536—8580. https://doi.org/10.1021/acs.chemrev.9b00766
Yan, J., Kong, L., Ji, Y., White, J., Li, Y., Zhang, J., An, P., Liu, S., Lee, S. T., & Ma, T. (2019). Single atom tungsten doped ultrathin alpha-Ni(OH)2 for enhanced electrocatalytic water oxidation. Nature Communications, 10(1), 2149. https://doi.org/10.1038/s41467-019-09845-z
Yu, Y., Zhou, J., & Sun, Z. (2020). Novel 2D transition‐metal carbides: ultrahigh performance electrocatalysts for overall water splitting and oxygen reduction. Advanced Functional Materials, 30(47), 200570. https://doi.org/10.1002/adfm.202000570
Zahra, R., Pervaiz, E., Yang, M., Rabi, O., Saleem, Z., Ali, M., & Farrukh, S. (2020). A review on nickel cobalt sulphide and their hybrids: Earth abundant, pH stable electro-catalyst for hydrogen evolution reaction. International Journal of Hydrogen Energy, 45(46), 24518—24543. https://doi.org/10.1016/j.ijhydene.2020.06.236
Zhang, X., Hou, F., Li, H., Yang, Y., Wang, Y., Liu, N., & Yang, Y. (2018). A strawsheave-like metal organic framework Ce-BTC derivative containing high specific surface area for improving the catalytic activity of CO oxidation reaction. Microporous and Mesoporous Materials, 259, 211—219. https://doi.org/https://doi.org/10.1016/j.micromeso.2017.10.019
Zhang, X., Hou, F., Yang, Y., Wang, Y., Liu, N., Chen, D., & Yang, Y. (2017). A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation. Applied Surface Science, 423, 771—779. https://doi.org/https://doi.org/10.1016/j.apsusc.2017.06.235
Zhou, H. C., Long, J. R., & Yaghi, O. M. (2012). Introduction to metal-organic frameworks. Chemical Reviews, 112(2), 673—674. https://doi.org/10.1021/cr300014x
Zou, Z., Cai, M., Zhao, X., Huang, J., Du, J., & Xu, C. (2019). Defective metal–organic framework derivative by room-temperature exfoliation and reduction for highly efficient oxygen evolution reaction. Journal of Materials Chemistry A, 7(23), 14011—14018. https://doi.org/10.1039/c9ta02349f
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