Luminol is one of the most widely
used electrochemiluminescence
(ECL) reagents, yet the detailed mechanism and kinetics of the electrochemical
oxidation of luminol remain unclear. We propose a model that describes
the electrochemical oxidation of luminol as multiple electron transfer
reactions followed by an irreversible chemical reaction, and we applied
a finite element method simulation to analyze the electron transfer
kinetics in alkaline solutions. Although negligible at higher pH values,
the adsorption of luminol on the glassy carbon electrode became noticeable
in a solution with pH = 12. Additionally, various types of adsorption
behaviors were observed for luminol derivatives and analogues, indicating
that the molecular structure affected not only the oxidation but also
the adsorption process. The adsorption effect was analyzed through
a model with a Langmuir isotherm to show that the saturated surface
concentration as well as the reaction kinetics increased with decreasing
pH, suggesting a competition for the active sites between the molecule
and OH–. Moreover, we show that the ECL intensity
could be boosted through the adsorption effect by collecting the ECL
intensity generated through the electrochemical oxidation of luminol
and a luminol analogue, L012, in a solution with pH = 13. In contrast
with luminol, a significant adsorption effect was observed for L012
at pH = 13, and the ECL intensity was enhanced by the adsorbed species,
especially at higher scan rates. The magnitude of the enhancement
of the ECL intensity matched well with the simulation using our model.