Orbital interactions and chemical reactivity of metal particles and metal surfaces

A review is presented with 101 refs. on chem. bonding to metal surfaces and small metal particles demonstrating the power of symmetry concepts to predict changes in chem. bonding. Ab-initio calcns. of chemisorption to small particles, as well as semiempirical extended Hueckel calcns. applied to the study of the reactivity of metal slabs are reviewed. On small metal particles, classical notions of electron promotion and hybridization are found to apply. The surroundings of a metal atom (ligands in complexes, other metal atoms at surfaces), affect bonding and reactivity through the prehybridization they induce. A factor specific for large particles and surfaces is the required localization of electrons on the atoms involved in the metal surface bond. At the surface, the bond energy is found to relate to the grou8p orbital local d. of states at the Fermi level. The use of this concept is extensively discussed and illustrated for chemisorption of CO and dissocn. of NO on metal surfaces. A discussion is given of the current decompn. schemes of bond energies and related concepts (exchange (Pauli)-repulsion, polarization, charge transfer). The role of non-orthogonality of fragment orbitals and of kinetic and potential energy for Pauli repulsion and (orbital) polarization is analyzed. Numerous examples are discussed to demonstrate the impact of those concepts on chem. bonding theor

Coupling between adjacent crystal planes in heterogeneous catalysis by propagating reaction–diffusion waves

UNDERSTANDING of the mechanisms and kinetics of heterogeneous catalytic reactions has come largely from the study of gas–solid interactions on well defined single-crystal surfaces1,2. But real catalysts usually consist of nanometre-sized particles on which several different crystal planes are exposed. In general, it has been assumed that their properties can be regarded as a superposition of the contributions from each individual structural element. Here we show that this assumption may be invalid, even qualitatively, in certain cases. We have studied the oxidation of hydrogen on platinum surfaces at low pressure and room temperature. On a macroscopic Pt(lOO) single crystal the reaction reaches a steady state with a uniform distribution of adsorbates. But on the platinum tip of a field ion microscope, on which several different crystal planes are exposed, the reaction has a very different character. The tip contains a region of the (100) plane just 40 nm in diameter, on which the reaction rate displays sustained temporal oscillations. This effect is associated with continuously changing distributions of the adsorbed species in the form of propagating waves, which are generated by coupling of reactions occurring on adjacent crystal planes. This kind of interaction between different crystal planes may exert a profound influence on the kinetics of heterogeneous catalysis