Studies of the Correlation of Electrode Kinetics with Molecular Structure

摘要

The overall objective is to develop our understanding of the connections between the kinetics and mechanisms of heterogeneous electron-transfer reactions at metal-electrolyte interfaces and the molecular structure of the reactant and the interfacial region. We have chiefly focussed attention on transition-metal redox couples, especially Co(III)/(II), Cr(III)/(II), and Ru(III)/(II) containing adsorbing inorganic and organic ligands at a number of electrocatalytic solid surfaces, especially silver, platinum, and gold, as well as at mercury electrodes. By combining electrochemical kinetic and reactant adsorption thermodynamic measurements, along with in situ vibrational spectroscopic studies using Surface-Enhanced Raman Scattering (SERS), the various catalytic influences exerted by the metal interface upon the energetics of electrode reactions have been probed in detail.