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Abstract Elucidating the mechanisms of electrochemiluminescence (ECL) generation is crucial for developing novel ECL systems, designing new luminophores and coreactants, and expanding the application of ECL in different fields. Diverse methods have been developed so far for this purpose, among which spatially resolved measurements using ECL microscopy (ECLM), scanning electrochemical microscopy (SECM) and ECL self‐interference spectroscopy (ECLIS), are particularly valuable in terms of their ability to measure the distribution of excited luminophores and coreactant radicals. This review aims to provide an overview of research progress on deciphering the mechanisms of ECL by spatially resolved measurements. The reaction pathways for ECL generation are briefly introduced and then the advances in understanding the mechanisms of ECL reaction in solutions and on the surface of microbeads are summarized. A personal perspective covering both mechanisms and challenges is finally presented.
Wang et al. (Wed,) studied this question.