Earth-Abundant Metals-Based Catalysts for Hydrogen Evolution Reaction
K. Keerthi, E.A. Lohith, Sada Venkateswarlu, K. Siva Kumar, N.V.V. Jyothi
A crucial step in the search for sustainable energy is the hydrogen evolution reaction (HER), especially when it comes to water splitting for the production of hydrogen. Because of their exceptional stability and efficiency, platinum-group metals (PGMs) have long been the standard catalyst for HER. However, the hunt for substitute catalysts made from earthly plentiful metals has been fueled by the rarity and high cost of PGMs. This chapter provides a thorough overview of recent developments in the creation of metal-based catalysts for HER that are abundant on earth. We explore the structural design approaches, synthesis procedures, and catalytic properties of different metal-based catalysts, such as those made from transition metals, their compounds, and alloys. Particular focus is placed on surface engineering techniques, electronic structural alterations, and mechanistic discoveries that have significantly improved their catalytic efficiency. This chapter also addresses the difficulties in maintaining these catalysts’ activity and durability under operating settings and provides insights into potential future research avenues for the goal of producing hydrogen in a way that is both affordable and sustainable.
Keywords
Earth-Abundant Metals, Catalysts, Water Splitting, HER
Published online 9/10/2025, 19 pages
Citation: K. Keerthi, E.A. Lohith, Sada Venkateswarlu, K. Siva Kumar, N.V.V. Jyothi, Earth-Abundant Metals-Based Catalysts for Hydrogen Evolution Reaction, Materials Research Foundations, Vol. 179, pp 320-338, 2025
DOI: https://doi.org/10.21741/9781644903711-11
Part of the book on Applications for Earth-Abundant Transition Metals
References
[1] U. Shankar, A. Basu, Energy and Sustainability, In Oxford University Press eBooks 2024 pp. 767-782. https://doi.org/10.1093/oxfordhb/9780198884682.013.43
[2] F. Martins, C. Felgueiras, M. Smitkova, N. Caetano, Analysis of Fossil Fuel Energy Consumption and Environmental Impacts in European Countries, Energies, 2019, 12(6), pp. 964. https://doi.org/10.3390/en12060964
[3] G. Shi, T. Tano, D. A. Tryk, A. Iiyama, M. Uchida, K. Terao, H. Osada, M. Yamaguchi, K. Tamoto, K. Kakinuma, Nanostructured Pt-NiFe Oxide Catalyst for Hydrogen Evolution Reaction in Alkaline Electrolyte Membrane Water Electrolyzers, ACS Catalysis, 2024, 14(12), pp. 9460-9468. https://doi.org/10.1021/acscatal.4c01685
[4] S. Xie, H. Dong, X. Peng, P.K. Chu, Non-precious Electrocatalysts for the Hydrogen Evolution Reaction, Innovation discovery, 2024, 1(2), pp. 11. https://doi.org/10.53964/id.2024011
[5] G.K. Gebremariam, A.Z. Jovanović, I.A. Pašti, The Effect of Electrolytes on the Kinetics of the Hydrogen Evolution Reaction. Hydrogen, 2023, 4(4), pp. 776-806. https://doi.org/10.3390/hydrogen4040049
[6] Z. Hou, Y. Guo, F. Chen, X. Chi, J. Jiao, W. Zhang, S. Zhou, Z. Hu, Performance analysis of hydrogen storage systems with oxygen recuperation for intermittent renewable energy generation system, Journal of Energy Storage, 2024, 86, 111150. https://doi.org/10.1016/j.est.2024.111150
[7] Z. Xie, Q. Jin, G. Su, W. Lu, A Review of Hydrogen Storage and Transportation: Progresses and Challenges. Energies, 2024 17(16), 4070. https://doi.org/10.3390/en17164070
[8] M. Younas, M. Yar, H. AlMohamadi, T. Mahmood, K. Ayub, A.L. Khan, M. Yasin, M.A. Gilani, A rational design of covalent organic framework supported single atom catalysts for hydrogen evolution reaction: A DFT study. International Journal of Hydrogen Energy, 2023, 51, pp. 758-773. https://doi.org/10.1016/j.ijhydene.2023.07.062
[9] Y. Wang, T. Wang, H. Arandiyan, G. Song, H. Sun, Y. Sabri, C. Zhao, Z. Shao, S. Kawi, Advancing Catalysts by Stacking Fault Defects for Enhanced Hydrogen Production: A Review. Advanced Materials, 2024 https://doi.org/10.1002/adma.202313378
[10] A. Bazan, G. García, A.M. Baena-Moncada, E. Pastor, Ni Foam-Supported NiMo Catalysts for the HER, Electrochemical Society, MA2022-0, 2022, 1(34), 1390. https://doi.org/10.1149/MA2022-01341390mtgabs
[11] X. Gao, S. Dai, Y. Teng, Q. Wang, Z. Zhang, Z. Yang, M. Park, H. Wang, Z. Jia, Y. Wang, Y. Yang, Ultra-Efficient and Cost-Effective Platinum Nanomembrane Electrocatalyst for Sustainable Hydrogen Production. Nano-Micro Letters, 2024, 16(1). https://doi.org/10.1007/s40820-024-01324-5
[12] H. Niu, Q. Wang, C. Huang, M. Zhang, Y. Yan, T. Liu, W. Zhou, Noble Metal-Based Heterogeneous Catalysts for Electrochemical Hydrogen Evolution Reaction, Applied Sciences, 2023, 13(4), 2177 https://doi.org/10.3390/app13042177
[13] K. Cheng, L.C.J. Smulders, L.L. Van Der Wal, J. Oenema, J.D. Meeldijk, N.L. Visser, G. Sunley, T. Roberts, Z. Xu, E. Doskocil, H. Yoshida, Y. Zheng, J. Zečević, P. De Jongh, K.P. De Jong, Maximizing noble metal utilization in solid catalysts by control of nanoparticle location. Science, 2022, 377(6602), 204-208. https://doi.org/10.1126/science.abn8289
[14] J. Yu, F.G. Pineda, J.R. Galan-Mascaros, Earth-Abundant Metal Oxides as Oxygen Evolution Electrocatalysts in 1 M H2SO4, Meeting Abstracts (Electrochemical Society. CD-ROM), 2024, MA2024-01(34), 1782. https://doi.org/10.1149/MA2024-01341782mtgabs
[15] G. Xu, C. Cai, W. Zhao, Y. Liu, T. Wang, Rational design of catalysts with earth‐abundant elements. Wiley Interdisciplinary Reviews Computational Molecular Science, 2022, 13(4). https://doi.org/10.1002/wcms.1654
[16] P. Wang, J. Zheng, X. Xu, Y. Zhang, Q. Shi, Y. Wan, S. Ramakrishna, J. Zhang, L. Zhu, T. Yokoshima, Y. Yamauchi, Y. Long, Unlocking Efficient Hydrogen Production: Nucleophilic Oxidation Reactions Coupled with Water Splitting. Advanced Materials. 2024, 36, 2404806. https://doi.org/10.1002/adma.202404806
[17] N. Giddaerappa, N.N. Kousar, N.S. Kumar, M. Hojamberdiev, L.K. Sannegowda, Substrate-Driven Electrocatalysis of Natural and Earth-Abundant Pyrite Towards Oxygen Evolution Reaction. Electrochimica Acta, 2023, 475, 143575. https://doi.org/10.1016/j.electacta.2023.143575
[18] H. Nemamcha, N. Vu, D.S. Tran, C. Boisvert, D.D. Nguyen, P. Nguyen-Tri, Recent progression in MXene-based catalysts for emerging photocatalytic applications of CO2 reduction and H2 production: A review, The Science of the Total Environment, 2024, 172816. https://doi.org/10.1016/j.scitotenv.2024.172816
[19] Y. Lan, H. He, C. Liu, J. Qin, L. Luo, F. Zhu, Y. Zhao, J. Zhang, L. Yang, H. Huang, Ultrasmall Pd nanocrystals confined into Co-based metal organic framework-decorated MXene nanoarchitectures for efficient methanol electrooxidation, Journal of Power Sources, 2024, 603, 234438. https://doi.org/10.1016/j.jpowsour.2024.234438
[20] P. Rodrigues, H. Bangali, E.A.M. Saleh, S.R. Hamza, B.S. Mirzaev, F. Ghali, B.M. Hussien, S.B. Hussein, R.T. Habash, Y.F. Mustafa, Metal-organic framework/MXene nanohybrid composites as an emerging electrochemical sensing platform for food safety and biomedical monitoring: From synthesis to application, Electrochimica Acta, 2024, 494, 144424. https://doi.org/10.1016/j.electacta.2024.144424
[21] N. Kitchamsetti, J.S. Cho, A roadmap of recent advances in MXene@MOF hybrids, its derived composites: Synthesis, properties, and their utilization as an electrode for supercapacitors, rechargeable batteries and electrocatalysis, Journal of Energy Storage, 2024, 80, 110293. https://doi.org/10.1016/j.est.2023.110293
[22] Z. Sun, R. Wang, V.E. Matulis, K. Vladimir, K. Structure, Synthesis, and Catalytic Performance of Emerging MXene-Based Catalysts, Molecules, 2024, 29(6), 1286. https://doi.org/10.3390/molecules29061286
[23] G. Maduraiveeran, M. Sasidharan, W. Jin, Earth-abundant transition metal and metal oxide nanomaterials: Synthesis and electrochemical applications, Progress in Materials Science, 2019, 106, 100574. https://doi.org/10.1016/j.pmatsci.2019.100574
[24] M.A. Khan, S. Khan, S. Sengupta, B.N. Mongal, S. Naskar, Earth abundant transition metal complexes as molecular water oxidation catalysts, Coordination Chemistry Reviews, 2024, 504, 215679. https://doi.org/10.1016/j.ccr.2024.215679
[25] P.J. Chirik, K.M. Engle, E.M. Simmons, S.R. Wisniewski, Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis. Organic Process Research & Development, 2023, 27(7), pp.1160-1184. https://doi.org/10.1021/acs.oprd.3c00025
[26] S. Kment, A. Bakandritsos, I. Tantis, H. Kmentová, Y. Zuo, O. Henrotte, A. Naldoni, M. Otyepka, R.S. Varma, R. Zbořil, Single Atom Catalysts Based on Earth-Abundant Metals for Energy-Related Applications. Chemical Reviews, 2024. https://doi.org/10.1021/acs.chemrev.4c00155
[27] A.M. Sadeq, R.Z. Homod, A.K. Hussein, H. Togun, A. Mahmoodi, H.F. Isleem, A.R. Patil, A.H. Moghaddam, Hydrogen energy systems: Technologies, trends, and future prospects. The Science of the Total Environment, 2024, 939, 173622. https://doi.org/10.1016/j.scitotenv.2024.173622
[28] M.A. Habib, G.A. Abdulrahman, A.B. Alquaity, N.A. Qasem, Hydrogen combustion, production, and applications: A review. Alexandria Engineering Journal, 2024, 100, 182-207. https://doi.org/10.1016/j.aej.2024.05.030
[29] S.E. Hosseini, Hydrogen fuel, a game changer for the world’s energy scenario. International Journal of Green Energy, 2023, 21(6), pp.1366-1382. https://doi.org/10.1080/15435075.2023.2244050
[30] N. Victor, C. Nichols, Future of Hydrogen in the U.S. Energy Sector: MARKAL Modeling Results, Applications in Energy and Combustion Science, 2024, 100259. https://doi.org/10.1016/j.jaecs.2024.100259
[31] R.M. Bullock, J.G. Chen, L. Gagliardi, P.J. Chirik, O.K. Farha, C.H. Hendon, C.W. Jones, J.A. Keith, J. Klosin, S.D. Minteer, R.H. Morris, A.T. Radosevich, T.B. Rauchfuss, N.A. Strotman, A. Vojvodic, T.R. Ward, J.Y. Yang, Y. Surendranath, Using nature’s blueprint to expand catalysis with Earth-abundant metals. Science, 2020, 369(6505). https://doi.org/10.1126/science.abc3183
[32] F. Wu, Z. Chen, H. Wu, F. Xiao, S. Du, C. He, Y. Wu, Z. Ren, In Situ Catalytic Etching Strategy Promoted Synthesis of Carbon Nanotube Inlaid with Ultrasmall FeP Nanoparticles as Efficient Electrocatalyst for Hydrogen Evolution, ACS Sustainable Chemistry & Engineering, 2019, 7(15), pp.12741-12749. https://doi.org/10.1021/acssuschemeng.9b00998
[33] A. Ambrosi, X. Chia, Z. Sofer, M. Pumera, Enhancement of electrochemical and catalytic properties of MoS2 through ball-milling, Electrochemistry Communications, 2015, 54, pp.36-40. https://doi.org/10.1016/j.elecom.2015.02.017
[34] L. Zhang, L. Ji, Z. Yao, N. Yan, Z. Sun, X. Yang, X. Zhu, S. Hu, L. Chen, Facile synthesized Fe nanosheets as superior active catalyst for hydrogen storage in MgH2, International Journal of Hydrogen Energy, 2019, 44(39), pp.21955-21964. https://doi.org/10.1016/j.ijhydene.2019.06.065
[35] F. Davodi, E. Mühlhausen, D. Settipani, E. Rautama, A. Honkanen, S. Huotari, G. Marzun, P. Taskinen, T. Kallio, T. Comprehensive study to design advanced metal-carbide@garaphene and metal-carbide@iron oxide nanoparticles with tunable structure by the laser ablation in liquid, Journal of Colloid and Interface Science, 2019, 556, pp.180-192. https://doi.org/10.1016/j.jcis.2019.08.056
[36] L. Zhang, K. Xiong, Y. Nie, X. Wang, J. Liao, Z. Wei, Sputtering nickel-molybdenum nanorods as an excellent hydrogen evolution reaction catalyst, Journal of Power Sources, 2015, 297, pp.413-418. https://doi.org/10.1016/j.jpowsour.2015.08.004
[37] B. Gao, X. Du, Y. Ma, Y. Li, Y. Li, S. Ding, Z. Song, C. Xiao, 3D flower-like defected MoS2 magnetron-sputtered on candle soot for enhanced hydrogen evolution reaction. Applied Catalysis B Environment and Energy, 2019, 263, 117750. https://doi.org/10.1016/j.apcatb.2019.117750
[38] S.A. Abbas, M.I. Iqbal, S. Kim, K. Jung, K. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution, Electrochimica Acta, 2017, 227, pp. 382-390. https://doi.org/10.1016/j.electacta.2017.01.039
[39] B.T. Jebaslinhepzybai, T. Partheeban, D.S. Gavali, R. Thapa, M. Sasidharan, One-pot solvothermal synthesis of Co2P nanoparticles: An efficient HER and OER electrocatalysts, International Journal of Hydrogen Energy, 2021, 46(42), pp. 21924-21938. https://doi.org/10.1016/j.ijhydene.2021.04.022
[40] D. Chanda, J. Hnát, M. M. Paidar, J. Schauer, K. Bouzek, Synthesis and characterization of NiFe2O4 electrocatalyst for the hydrogen evolution reaction in alkaline water electrolysis using different polymer binders, Journal of Power Sources, 2015, 285, pp. 217-226. https://doi.org/10.1016/j.jpowsour.2015.03.067
[41] K. Uma, E. Muniranthinam, S. Chong, T.C. Yang, J. Lin, Fabrication of Hybrid Catalyst ZnO Nanorod/α-Fe2O3 Composites for Hydrogen Evolution Reaction, Crystals, 2020, 10(5), 356. https://doi.org/10.3390/cryst10050356
[42] R. Miao, B. Dutta, S. Sahoo, J. He, W. Zhong, S.A. Cetegen, T. Jiang, S.P. Alpay, S.L. Suib, Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution. Journal of the American Chemical Society, 2017, 139(39), pp. 13604-13607. https://doi.org/10.1021/jacs.7b07044
[43] P. Yu, F. Wang, T.A. Shifa, X. Zhan, X. Lou, F. Xia, J. He, Earth abundant materials beyond transition metal dichalcogenides: A focus on electrocatalyzing hydrogen evolution reaction. Nano Energy, 2019, 58, pp. 244-276. https://doi.org/10.1016/j.nanoen.2019.01.017
[44] Y. Du, Z. Wang, H. Li, Y. Han, Y. Liu, Y. Yang, Y. Liu, L. Wang, Controllable synthesized CoP-MP (M=Fe, Mn) as efficient and stable electrocatalyst for hydrogen evolution reaction at all pH values, International Journal of Hydrogen Energy, 2019, 44(36), pp. 19978-19985. https://doi.org/10.1016/j.ijhydene.2019.06.036
[45] H.B. Wu, B.Y. Xia, L. Yu, X. Yu, X.W. Lou, Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production. Nature Communications, 2015, 6(1). https://doi.org/10.1038/ncomms7512
[46] Z. Zhang, J. Ran, E. Fan, S. Zhou, D. Chai, W. Zhang, M. Zhao, G. Dong, Mesoporous CoMoO4 hollow tubes derived from POMOFs as efficient electrocatalyst for overall water splitting, Journal of Alloys and Compounds, 2023, 968, 172169. https://doi.org/10.1016/j.jallcom.2023.172169
[47] B. Shen, H. Huang, Y. Jiang, Y. Xue, H. He, 3D interweaving MXene-graphene network-confined Ni-Fe layered double hydroxide nanosheets for enhanced hydrogen evolution, Electrochimica Acta, 2022, 407, 139913. https://doi.org/10.1016/j.electacta.2022.139913
[48] R. Wang, P. Sun, Q. Yuan, R. Nie, X. Wang, MOF-derived cobalt-embedded nitrogen-doped mesoporous carbon leaf for efficient hydrogen evolution reaction in both acidic and alkaline media. International Journal of Hydrogen Energy, 2019, 44(23), pp.11838-11847. https://doi.org/10.1016/j.ijhydene.2019.03.029
[49] C. Liao, C. Huang, J.C.S. Wu, Hydrogen Production from Semiconductor-based Photocatalysis via Water Splitting. Catalysts, 2012, 2(4), pp. 490-516. https://doi.org/10.3390/catal2040490
[50] S. Pitchaimuthu, K. Sridharan, S. Nagarajan, S. Ananthraj, P. Robertson, M.F. Kuehnel, A. Irabien, M. Maroto-Valer, Solar Hydrogen Fuel Generation from Wastewater-Beyond Photoelectrochemical Water Splitting: A Perspective, Energies, 2022, 15(19), 7399. https://doi.org/10.3390/en15197399
[51] B.M. Hunter, W. Hieringer, J.R. Winkler, H.B. Gray, A.M. Müller, Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity. Energy & Environmental Science, 2016, 9(5), pp. 1734-1743. https://doi.org/10.1039/C6EE00377J
[52] X. Liu, Y. Zhao, X. Yang, Q. Liu, X. Yu, Y. Li, H. Tang, T. Zhang, Porous Ni5P4 as a promising cocatalyst for boosting the photocatalytic hydrogen evolution reaction performance, Applied Catalysis B Environment and Energy, 2020, 275, 119144. https://doi.org/10.1016/j.apcatb.2020.119144
[53] A.G. Tamirat, W. Su, A.A. Dubale, C. Pan, H. Chen, D.W. Ayele, J. Lee, B. Hwang, (2015). Efficient photoelectrochemical water splitting using three dimensional urchin-like hematite nanostructure modified with reduced graphene oxide. Journal of Power Sources, 2015, 287, pp.119-128. https://doi.org/10.1016/j.jpowsour.2015.04.042
