Fundamentals of Electrocatalysis: which role play the nanostructures?

E. SANTOS AND W. SCHMICKLER

Giessen, Alemania

Conferencia; Gesellschaft Deutscher Chemiker, Electrochemistry: Crossing boundaries; 2008

Recently, we have proposed a unified model for electrochemical electron transferreactions on metals, which explicitly accounts for the electronic structure of theelectrode. Our approach applies the SKS-Hamiltonian [1] for concerted bond breakingand electron-transfer reactions at metal electrodes; it contains the contributions of themolecule, the metal which acts as a catalyst, the solvent and the correspondinginteractions between these subsystems. First calculations had been performed withinthe wideband approximation for the electronic structure of the metal and the extendedHückel approximation for the molecule [1]. Later, we have introduced idealized bandshapes [2]. Finally, we have performed calculations for a real system, namely thehydrogen oxidation reaction, including explicitly the band structure of different metalsobtained from the Density Functional Theory (DFT) [3].