A Tetranuclear NiII4O4 Cubane Molecular Complex as an Efficient Electrocatalyst for Oxygen Evolution Reaction: From Synthesis to Mechanistic Insights
Authors :- JA Bharatbhai, S Roy, A Dey, T Aziz, S Tothadi, M Bandhyopadhyay, S Das et al.
Publication :- Small (Nanoscience & Nanotechnology journal), Wiley, 2025
The oxygen evolution reaction (OER) is integral to electrochemical energy systems; however, its intrinsic sluggish kinetics necessitate the design of high-performance electrocatalysts to minimize overpotential, enhance the durability, and optimize the efficiency. Significant efforts have been dedicated to developing OER catalysts based on earth-abundant transition-metal complexes. Here, the efficacy of a tetranuclear cubane-cored Ni(II) complex, [Ni₄(LH)₄(MeOH)]·CHCl₃ (1), in OER is demonstrated. The complex is synthesized using a tetradentate Schiff-base ligand, [2-{(E)-(2-hydroxyphenylimino)methyl)-6-(hydroxymethyl)-4-methylphenol}], and characterized by single-crystal X-ray diffraction. The redox properties of complex 1 are evaluated by cyclic voltammetry in the solid state, which emphasize the quasireversible oxidation state of the Ni(II) metal center. The complex 1 is immobilized on activated carbon cloth (CC), referred as CC-1, which demonstrates efficient OER catalysis, subsequently activating to form the Ni(O)OH catalyst. The postreaction analysis including UV–vis, FTIR, scanning electron microscopy–energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy confirm the stability of molecular complex 1. The results demonstrate efficient OER catalysis with a low overpotential of 330 mV versus reversible hydrogen electrode and a Tafel slope of 64 mV dec−1, confirming an effective OER catalyst in alkaline medium with a deep understanding of the core reaction mechanisms.