Electrochemiluminescence of luminol in alkaline solution at a paraffin-impregnated graphite electrode

摘要

The behavior of luminol electrochemiluminescence (ECL) at a paraffin-impregnated graphite electrode (PIGE) at different applied potentials was studied. Five ECL peaks were observed at 0.31, 0.59, 1.09, 1.54, and -0.58 V versus SCE, respectively, being related to potential scan direction and ranges, N-2, O-2, pH of the solution, and KCl concentration. The emission spectra of various ECL peaks at different potentials showed that all ECL peaks were initiated by luminol reactions. X-ray diffraction demonstrated that a simple mixture was formed between graphite and paraffin. The fluorescence spectra on the surface of the PIGE suggested that certain groups on the graphite were oxidized when the positive potential was applied to the electrode. In the presence Of 02, three main ECL peaks were obtained in 0.1 mol/L KCl at pH 12.2. The ECL peak at 0.59 V with a shoulder is likely due to the reaction of luminol radicals with 02 and further electrooxidation of luminol radicals. The ECL peak at 1.54 V was suggested to be due to the electrooxidation of OH- to HO2- at higher potential and then to O-2(.-), which reacted with luminol to produce light emission. Moreover, the oxygen-containing functional groups formed by the oxidation of the surface of the graphite electrode might enhance the ECL. At -0.58 V, the dissolved oxygen in solution was reduced to 1102, resulting in light emission. At a potential higher than 1.64 V, ClO- was formed, leading to a broad emission wave and enhancement of the ECL peak at -0.58 V upon the reversal scan. Under nitrogen atmosphere, an ECL peak appeared at 1.09 V. At this potential, OH- was oxidized to 02, followed by the reaction with luminol to generate light emission. At pH 13.2 or 0.5 mol/L KCl, the shoulder of the ECL peak at 0.59 V became an ECL peak at 0.31 V. The conversion of luminol radicals into excited 3-aminophthalate may undergo two routes. Under these conditions, two routes might proceed at a different rate to form another ECL peak. It is concluded that luminol ECL could be readily excited by various oxygen-containing species electrogenerated at different applied potentials. Three strong ECL peaks obtained at different potentials on the PIGE might be of a potential to improve analytical selectivity and sensitivity for the detection of some analytes. [References: 21]