Nickel–cobalt oxalate as an efficient non-precious electrocatalyst for an improved alkaline oxygen evolution reaction

The quest for developing next-generation non-precious electrocatalysts has risen in recent times. Herein, we have designed and developed a low cost electrocatalyst by a ligand-assisted synthetic strategy in an aqueous medium. An oxalate ligand-assisted non-oxide electrocatalyst was developed by a simple wet-chemical technique for alkaline water oxidation application. The synthetic parameters for the preparation of nickel–cobalt oxalate (Ni(2.5)Co(5)C(2)O(4)) were optimized, such as the metal precursor (Ni/Co) ratio, oxalic acid amount, reaction temperature, and time. Microstructural analysis revealed a mesoporous block-like architecture for nickel–cobalt oxalate (Ni(2.5)Co(5)C(2)O(4)). The required overpotential of Ni(2.5)Co(5)C(2)O(4) for the alkaline oxygen evolution reaction (OER) was found to be 330 mV for achieving 10 mA cm(geo)(−2), which is superior to that of NiC(2)O(4), CoC(2)O(4), NiCo(2)O(4) and the state-of-the-art RuO(2). The splendid performance of Ni(2.5)Co(5)C(2)O(4) was further verified by its low charge transfer resistance, impressive stability performance, and 87% faradaic efficiency in alkaline medium (pH = 14). The improved electrochemical activity was further attributed to double layer capacitance (C(dl)), which indefinitely divulged the inferiority of NiCo(2)O(4) compared to Ni(2.5)Co(5)C(2)O(4) for the alkaline oxygen evolution reaction (OER). The obtained proton reaction order (ρ(RHE)) was about 0.80, thus indicating the proton decoupled electron transfer (PDET) mechanism for OER in alkaline medium. Post-catalytic investigation revealed the formation of a flake-like porous nanostructure, indicating distinct transformation in morphology during the alkaline OER process. Further, XPS analysis demonstrated complete oxidation of Ni(2+) and Co(2+) centres into Ni(3+) and Co(3+), respectively under high oxidation potential, thereby indicating active site formation throughout the microstructural network. Additionally, from BET-normalised LSV investigation, the intrinsic activity of Ni(2.5)Co(5)C(2)O(4) was also found to be higher than that of NiCo(2)O(4). Finally, Ni(2.5)Co(5)C(2)O(4) delivered a TOF value of around 3.28 × 10(−3) s(−1), which is 5.56 fold that of NiCo(2)O(4) for the alkaline OER process. This report highlights the unique benefit of Ni(2.5)Co(5)C(2)O(4) over NiCo(2)O(4) for the alkaline OER. The structure–catalytic property relationship was further elucidated using density functional theory (DFT) study. To the best of our knowledge, nickel–cobalt oxalate (Ni(2.5)Co(5)C(2)O(4)) was introduced for the first time as a non-precious non-oxide electrocatalyst for alkaline OER application.