CONICET | Buscador de Institutos y Recursos Humanos

The reduction of molecular oxygen in triplet and singlet spin states at metal electrodes is analyzed in the framework of quantum mechanical theory of charge transfer. Both outer- and inner-sphere mechanism is considered. Singlet oxygen is argued to be considerably more active in electron transfer processes. It is demonstrated that spin polarization may play a catalytic role, parallel with the effect of overlap of reactant orbitals with the d-band of a metal electrode. Our model is based on two main assumptions: (i) some metal surfaces favor the existence of singlet molecular oxygen in adsorbed state; and (ii) short-living singlet O2molecules may appear as intermediates at some reduction steps. These two reasons are expected to increase the local concentration of active singlet molecular oxygen in reaction layer.