Theory of Electrocatalysis: a unified model

E. SANTOS; W. SCMICKLER

Workshop; Workshop Ab Initio Electrochemistry - CECAM; 2010

INVITED LECTURE In the past, there have been several attempts to relate the catalytic activity of metals to their physical or chemical properties. Thus, phenomenological correlations have been established, with limited success. Purely chemical reactions can be well described by DFT alone, but all proper electrochemical reactions involve electron transfer, in which the solvent plays a crucial role. Recently, we have proposed a unified model for electrochemical electron transfer reactions on metals, which explicitly accounts for the the contributions of the molecule, the metal which acts as a catalyst, the solvent and the corresponding interactions between these subsystems.It combines elements of the Marcus–Hush theory [1] of electron transfer, the Anderson–Newns model [2] for adsorption and DFT calculations to obtain some of the parameters to be inserted as input in the Santos–Koper–Schmickler (SKS)–Hamiltonian [3] for electrochemical bond-breaking reactions.