A Carbonate-Involved Amplification Strategy for Cathodic Electrochemiluminescence of Luminol Triggered by the Catalase-like CoO Nanorods

The lumiol-O₂ electrochemiluminescence (ECL) system constantly emits bright light at positive potential. Notably, compared with the anodic ECL signal of the luminol-O₂ system, the great virtues of cathodic ECL are that it is simple and causes minor damage to biological samples. Unfortunately, little emphasis has been paid to cathodic ECL, owing to the low reaction efficacy between luminol and reactive oxygen species. The state-of-the-art work mainly focuses on improving the catalytic activity of the oxygen reduction reaction, which remains a significant challenge. In this work, a synergistic signal amplification pathway is established for luminol cathodic ECL. The synergistic effect is based on the decomposition of H₂O₂ by catalase-like (CAT-like) CoO nanorods (CoO NRs) and regeneration of H₂O₂ by a carbonate/bicarbonate buffer. Compared with Fe₂O₃ nanorod (Fe₂O₃ NR)- and NiO microsphere-modified glassy carbon electrodes (GCEs), the ECL intensity of the luminol-O₂ system is nearly 50 times stronger when the potential ranged from 0 to -0.4 V on the CoO NR-modified GCE in a carbonate buffer solution. The CAT-like CoO NRs decompose the electroreduction product H₂O₂ into OH^· and O₂^·-, which further oxidize HCO₃^- and CO₃^2- to HCO₃^· and CO₃^·-. These radicals very effectively interact with luminol to form the luminol radical. More importantly, H₂O₂ can be regenerated when HCO₃^· dimerizes to produce (CO₂)₂*, which provides a cyclic amplification of the cathodic ECL signal during the dimerization of HCO₃^·. This work inspires developing a new avenue to improve cathodic ECL and deeply understand the mechanism of a luminol cathodic ECL reaction.