The effect of electrode material on the electrogenerated chemiluminescence of luminol

This paper reports on the oxidation of luminol and its concomitant electrogenerated chemiluminescence (ECL) which were studied at several electrode materials by voltammetry and chronoamperometry. The ECL intensity (I{sub ECL}) was inversely related to the activity of the electrodes. The lowest I{sub ECL}) was measured when luminol was oxidized to 3-aminophthalate (n {approx equal}4 eq mol{sup {minus}1}) at a nearly mass-transport limited rate at glassy carbon. The ECL kinetics were studied and the order of the reaction with respect to luminol was 3/2 at concentrations to ca. 1 mM when O{sub 2} was the coreactant. In the presence of H{sub 2}O{sub 2}, the ECL reaction was first order with respect to luminol. A reaction mechanism is proposed that is consistent with the inetic data and the inverse relationship between electrode activity and I{sub ECL}. The implications of these results are discussed with respect to imaging the spatial distribution of current density at electrode surfaces, including that of PbO{sub 2} films activated by adsorbed Bi(V). A value of 6.6 {times} 10{sup {minus}6} cm{sup 2} s{sup {minus}1} was determined for the diffusion coefficient of luminol in 0.1M NaOH.