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After an introductory analysis of terms and concepts in the field of electrocatalysis, a number of experimental examples are reported to illustrate various factors. In particular, Tafel slope and PZC of oxide electrodes are shown to be able to disentangle electronic from geometric factors. The points under discussion are: effect of particle size and methods of preparation, surface vs. bulk composition, primary vs. secondary effects with redox systems depending on the molecular structure of the couple, single crystal vs. polycrystalline surfaces. The last case is particularly relevant since for the first time “vicinal” faces of RuO2 are shown to behave at the extremes of the usually observed experimental picture.
Guerrini et al. (Sun,) studied this question.