  Unique catalytic potential of metal surfaces has encouraged a great number of
basic and applied studies. The manuscript highlights the general regularities
in a field on the grounds of strong interrelation between catalytic, kinetic
and thermodynamic behaviour of the reaction system. The trials of the catalytic
NH3 synthesis and the oscillatory NO+H2 reaction have revealed that the
thermodynamics of the local structure determines the properties and
multiplicity of the reaction intermediates enabling the peculiar macroscopic
kinetics and specific catalytic activity. Structure and activity of catalytic
sites are correlated within a realistic model, where total undercoordination of
adjacent surface atoms and enthalpy of local reaction is taken as a descriptor
for structure and activity, respectively. The model has specified the resonant
catalytic centers for NH3 synthesis on metal surfaces in close agreement with
experimental data. The basal planes of noble metals are less active than Fe-
and Ru-based catalysts, whereas an extraordinary activity of small Pt, Ir and
Rh clusters can be expected. A strong advantage of imperfections compared to
perfect areas in the surface wave nucleation is evaluated. Isothermal rate
oscillations in open heterogeneous catalytic reaction systems are expected
under the multiplicity of reaction intermediates fairly different in activity,
providing the steady state and reaction rout multiplicity. Switching between
active and inactive kinetic brunches gives rise to the explosive coverage
changeover that can be visualized as a traveling wave. A single pattern of
oscillations in the NO+H2 reaction includes the key role of intermediate NHad
species providing the catalytic removal of strongly bound nitrogen. The driving
forces, the feedback, and chemical interactions within the traveling waves are
clearly understood.

Materials Science