LAUSR

Reversible and specific adsorption of redox-active molecules from the electrolyte solution to the electrode surface is an important process and is often diagnosed by cyclic voltammetry (CV). The entire voltammogram, however, is rarely analyzed quantitatively, thereby completely missing or incorrectly extracting inherent information about the adsorption isotherm. Herein, we report CV measurements of the adsorption isotherm for ferrocene derivatives on the basal plane of highly oriented pyrolytic graphite (HOPG) to quantitatively understand the thermodynamics of ferrocene-HOPG and ferrocene-ferrocene interactions at HOPG/water interfaces. Specifically, reversible CV of (ferrocenylmethyl)trimethylammonium, ferrocenemethanol, and 1,1'-ferrocenedimethanol is obtained at 0.05-10 V/s to confirm that only reduced forms of ferrocene derivatives are adsorbed on HOPG. Finite element analysis of the entire voltammogram yields the Frumkin isotherm to separately parametrize ferrocene-HOPG and ferrocene-ferrocene interactions. Adsorption of all ferrocene derivatives is driven by similarly weak ferrocene-HOPG interactions with free energy changes of approximately -20 kJ/mol. Adsorption of ferrocenemethanol is strengthened by intermolecular hydrogen bonding, which is quantitatively represented by a free energy change of -8 kJ/mol for surface saturation and is qualitatively characterized by a pair of sharp adsorption and desorption peaks following a pair of diffusional peaks. By contrast, adsorption of (ferrocenylmethyl)trimethylammonium and 1,1'-ferrocenedimethanol remains weak because of electrostatic repulsion and weak hydrogen bonding, respectively, which correspond to the respective free energy changes of +0.7 and -3 kJ/mol for surface saturation. The unfavorable or weakly favorable intermolecular interactions broaden or narrow a diffusional peak during the forward scan, respectively, without yielding a post peak.