Surface structures of catalytic materials

Turning to non-metallic catalysts, photoluminescence studies of alkaline-earth oxides in dre near-ultra-violet region show excitation of electrons corresponding to duee types of surface sites for the oxide ions which dominate the surface sUmcture. These sites can be described as having different cation co-ordination, which is normally six in the bulk, depending on the surface location. Ions on a flat surface have a co-ordination number of 5 (denoted 5c), those on the edges 4 (4c), and dre kiirk sites have co-ordination number 3 (3c). The latter can be expected to have higher chemical reactivity than 4c and 5c sites, as was postulated for dre evaporation mechanism. 

The spectroscopic evidence suggests that on adsorption of CO, an adsorbed ion and a polymeric form of the CO molecule are formed thus 

The value of n in the polymeric adsorbed species (CO) is larger on the 3c sites than on die 4c and 5c sites. The CO2 molecule is much more suongly adsorbed, indicating ion formation on the oxide surface, and the evidence suggests 

An important property of the surface behaviour of oxides which contain transition metal ions having a number of possible valencies can be revealed by X-ray induced photoelectron spectroscopy. The energy spectrum of tlrese electrons give a direct measure of the binding energies of the valence electrons on the metal ions, from which the charge state can be deduced (Gunarsekaran et al., 1994). 

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