The Bronsted-Evans-Polanyi relation and the volcano plot for ammonia synthesis over transition metal catalysts

Using density functional calculations we show that there is an essentially linear relationship between the activation energy for N-2 dissociation and the binding energy of atomic nitrogen on a range of transition metal surfac es. This relation, known as the Bronsted-Evans-Polanyi relation, is further shown to depend on the structure of the active site. The consequences of t he Bronsted-Evans-Polanyi relation in terms of the kinetics of the ammonia synthesis process under industrial conditions are discussed, and it is show n that the relation leads to a volcano-type dependence of the catalytic act ivity on the nitrogen heat of adsorption. The results show that density fun ctional calculations can predict the relative catalytic activity of differe nt transition metals. (C) 2001 Academic Press.