Electronic Effect and Key Intermediates in Electrochemical Ammonia Oxidation With Mn–Salen Complexes

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Abstract
Ammonia (NH 3 ) has emerged as a promising carbon‐free fuel and hydrogen carrier, offering a potential solution to meet growing global energy demands. In this study, we investigate the role of ligand electronic effects in a series of Mn–salen electrocatalysts for the ammonia oxidation reaction (AOR) in nonaqueous media. Our results reveal that electron‐withdrawing substituents promote an earlier onset potential and enhanced catalytic activity. A high‐valent nitrido‐manganese (V) salen species is identified as a key reaction intermediate through mass spectrometry during electrolysis, which undergoes nucleophilic attack by NH 3 under oxidative conditions to produce nitrogen (N 2 ). We also examined how solvent and electron‐transfer redox mediators affect the reaction. While the solvent shows no significant impact on catalytic performance, the use of a mediator markedly enhances reaction kinetics. Furthermore, the salen catalyst was evaluated for AOR in aqueous conditions, demonstrating an onset potential of 1.65 V versus RHE along with appreciable Faradaic efficiencies for N 2 and H 2 production of 93.6% ± 4.5% and 98.9% ± 1.7%, respectively, making it one of the few examples of selective AOR in aqueous medium.

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