Liquid-Phase Cyclic Chemiluminescence for the Identification of Cobalt Speciation

Accurate discrimination of metal species is a significant analytical challenge. Herein, we propose a novel methodology based on liquid-phase cyclic chemiluminescence (CCL) for the identification of cobalt speciation. The CCL multistage signals (I) of the luminol-H₂O₂ reaction catalyzed by different cobalt species have different decay coefficients k. Thereby, we can facilely identify various cobalt species according to the distinguishable k values, including the complicated and structurally similar cobalt complexes, such as analogues of [Co(NH₃)₅X] (X = Cl^-, H₂O, and NH₃), Co(II) porphyrins, and bis(2,4-pentanedione) cobalt(II) derivatives. Especially, the number of substituent atoms also influences the k value greatly, which allows excellent discrimination between complexes that only have a subtle difference in the substituent group. In addition, linear discriminant analysis based on I provides a complementary solution to improve the differentiating ability. We performed density functional theory calculations to investigate the interaction mode of H₂O₂ over cobalt species. A close negative correlation between the adsorption energy and the k value is observed. Moreover, the calculation of energy evolutions of H₂O₂ decomposition into a double hydroxide radical shows that a high level of consistency exists between the activation energy barrier and the k value. The results further demonstrate that the decay coefficient of the CCL multistage signal is associated with the catalytic reactivity of the cobalt species. Our work not only broadens the application of chemiluminescence but also provides a complementary technology for speciation analysis.