Catalysis of electron transfer at metal

ELIZABETH SANTOS ANDWOLFGANG SCHMICKLER

CATALYSIS IN ELECTROCHEMISTRY: FROM FUNDAMENTAL ASPECTS TO STRATEGIES FOR FUELL CELLS DEVELOPMENT:

Año: 2009;

In our work, which we will report below, we have taken a different approach. As our basis, we have taken a model Hamiltonian proposed by Santos, Koper and Schmickler (SKS) [3, 4], which contains the essential interactions, including the interaction of the reactants with the solvent. The resulting model explains the course of an electron transfer and suggests, how a strong interaction of the reactant with a metal d band can catalyze the reaction. For the application to real systems, we have obtained the relevant parameters from DFT calculations as far as possible. We will start by briefly reviewing the theory of outer-sphere electron transfer in order to present the basics. Next we explain, how the transfer can be catalyzes by a metal electrode, and illustrate this by model calculations both for simple and for bond-breaking electron transfer. Finally, we will apply our theory to the hydrogen reaction, and compare our calculations with experimental data. We will keep the presentation as simple as possible, relegating the SKS Hamiltonian, on which much of our work is based, to the appendix.d band can catalyze the reaction. For the application to real systems, we have obtained the relevant parameters from DFT calculations as far as possible. We will start by briefly reviewing the theory of outer-sphere electron transfer in order to present the basics. Next we explain, how the transfer can be catalyzes by a metal electrode, and illustrate this by model calculations both for simple and for bond-breaking electron transfer. Finally, we will apply our theory to the hydrogen reaction, and compare our calculations with experimental data. We will keep the presentation as simple as possible, relegating the SKS Hamiltonian, on which much of our work is based, to the appendix.