Ni-Based Metal Organic Framework-Derived Electrocatalyst for Hydrogen Evolution in Alkaline Media

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Ni-based materials are among the most active platinum group metal-free (PGM-free) electrocatalysts for hydrogen evolution reaction (HER) in alkaline media. [1] Such catalysts can be obtained by various synthesis approaches, which include the use of metal-organic frameworks (MOFs) as precursors. MOFs offer a well-defined structure, high surface area, and tunable chemistry, which together make them especially suitable as catalyst precursors. In water splitting electrolysis, hydrogen, carbon, (nitrogen), and oxygen-containing organic linkers, such as 1,3,5-benzenetricarboxylic acid, have been combined with nickel nodes to obtain Ni-based electrocatalyst precursors. [2, 3, 4] Expanding on our previous work, [5] we will report on the use of Ni-MOFs as HER catalyst precursors, containing underexplored organic ligands such as 1,3,5-tris(4-carboxyphenyl)benzene, 2,5-dihydroxyterephthalic acid, and 4,4’-biphenyldicarboxylic acid. In this work, the Ni-based MOFs were synthesized by a solvothermal method by mixing nickel salt and organic ligands. The resulting MOF powder was then heat-treated at various temperatures. The physicochemical properties of the resulting catalysts were assessed using transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) to elucidate the influence of temperature and organic ligands on the catalyst morphology, composition, thermal stability, and HER performance. Electrochemical HER measurements were conducted using a rotating disk electrode in 1.0 M KOH solution. Catalyst activity was found to strongly depend on the type of organic linker and heat-treatment temperature, with active materials revealing promising HER overpotentials not exceeding 90 mV at 10 mA cm -2 . Acknowledgement This work was supported by the Center for Alkaline-based Energy Solutions (CABES), an Energy Frontier Research Center (EFRC) supported by the U.S. Department of Energy under Grant DE-SC0019445. References [1] D. M. Sayed et al., ACS Appl. Energy Mater. , 8 , 10949 (2025). [2] T. Wang et al., J. Mater. Chem. A , 3 , 16435 (2015). [3] L. Wang et al., ACS Appl. Mater. Interfaces , 8 , 16736 (2016). [4] M. Salmanion et al., Inorg. Chem. , 61 , 5112 (2022). [5] H. Zhang and P. Zelenay, ECS Meeting Abstracts , MA2024-02 , 2810 (2024).

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