Correlation between catalytic activity and bonding and coordination number of atoms and molecules on transition metal surfaces: Theory and experimental evidence

Abstract

Correlation between catalytic activity and low-energy local electronic fluctuations in transition metals is proposed. A theory and calculations are presented which indicate that maximum electronic fluctuations take place at high-coordination metal sites. Either (i) atomically rough surfaces that expose to the reactant molecules atoms with large numbers of nonmagnetic or weakly magnetic neighbors in the first or second layer at the surface or (ii) stepped and kinked surfaces are the most active in carrying out structure-sensitive catalytic reactions. The synthesis of ammonia from N(2) and H(2) over iron and rhenium surfaces, (1)H(2)/(2)H(2) exchange over stepped platinum crystal surfaces at low pressures, and the hydrogenolysis (C-C bond breaking) of isobutane at kinked platinum crystal surfaces are presented as experimental evidence in support of the theory.