Systematic assessment of adsorption-coupled electron transfer toward voltammetric discrimination between concerted and non-concerted mechanisms

The electron transfer and specific adsorption of a redox-active molecule are coupled in many important electrode reactions. Herein, we report theoretical framework for the voltammetric discrimination concerted non-concerted mechanisms adsorption-coupled electron-transfer (ACET) In mechanism, an oxidant solution is simultaneously reduced adsorbed to deposit reductant on surface. Alternatively, steps mediated separately mechanism. Our model involves common step both ensure consistent properties redox couple. For simplicity, assumed weak that does not contribute current response. We predicted only kinetically controlled but also chemically reversible required identification reaction High scan rates were during cyclic voltammetry (CV) kinetic control step. Unique CV shapes, or characteristic changes therein, expected each mechanism oxidants reductants. modelled reduction benzyl chloride at Ag electrode. experimental this irreversible ACET was with either quantitatively validate our model. A has been demonstrated, it will be possible if requirements satisfied.