Tuning electrochemical water activation over NiIr single-atom alloy aerogels for stable electrochemiluminescence.

The anodic oxygen evolution reaction is a well-acknowledged side reaction in traditional aqueous electrochemiluminescence (ECL) systems due to the generation and surface aggregation of oxygen at the electrode, which detrimentally impacts the stability and efficiency of ECL emission. However, the effect of reactive oxygen species generated during water oxidation on ECL luminophores has been largely overlooked. Taking the typical luminol emitter as an example, herein, we employed NiIr single-atom alloy aerogels possessing efficient water oxidation activity as a prototype co-reaction accelerator to elucidate the relationship between ECL behavior and water oxidation reaction kinetics for the first time. By regulating the concentration of hydroxide ions in the electrolyte, the electrochemical oxidation processes of both luminol and water are finely tuned. When the concentration of hydroxide ions in electrolyte is low, the kinetics of water oxidation is attenuated, which limits the generation of oxygen, effectively mitigates the influence of oxygen accumulation on the ECL strength, and offers a novel perspective for harnessing side reactions in ECL systems. Finally, a sensitive and stable sensor for antioxidant detection was constructed and applied to the practical sample detection.