Coupled electron/proton transfer of galvinol attached to SAMs on gold electrodes

Literature Information

Publication Date 2001-05-15
DOI 10.1039/B101325O
Impact Factor 3.676
Authors

Harry O. Finklea, Robert M. Haddox


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Abstract

The theory for a 1-electron, 1-proton redox couple with potential-dependent transfer coefficients is tested using a self-assembled monolayer with attached galvinol/galvinoxyl redox couples on a gold electrode. The potential dependence of the transfer coefficients is derived from the Marcus density-of-states model of heterogeneous electron transfer. The pKa of surface-attached galvinol is 11.3. The predicted asymmetry in kinetically controlled cyclic voltammograms is observed at pHs lower than 11. Apparent standard rate constants between pH 10 and 13 are fitted to the theory to yield a standard rate constant of 4.5 × 10 s−1 for the deprotonated galvinol/galvinoxyl radical redox couple; this standard rate constant is comparable to the standard rate constant for ferrocene/ferricenium with the same number of atoms linking the redox center to the electrode. Anomalous behavior is seen for the apparent standard rate constants at pHs between 7 and 9.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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