Oxygen adatom reactivity surface

Support for the special reactivity of hot oxygen adatoms also came from Matsushima s temperature-programmed desorption study4 of CO oxidation at Pt(lll), when CO and 02 were coadsorbed at low temperature with C02 desorbed at 150 K, the temperature at which 02 dissociates. This temperature is some 150 K lower than that for C02 formation when oxygen is preadsorbed (thermally accommodated) at the Pt(lll) surface. 

Keywords Atomic scale characterization surface structure epoxidation reaction 111 cleaved silver surface oxide STM simulations DFT slab calculations ab initio phase diagram free energy non-stoichiometry oxygen adatoms site specificity epoxidation mechanism catalytic reactivity oxametallacycle intermediate transition state catalytic cycle. 

Impurity adatoms, such as H, N and O, have a dramatic influence on measured accommodation coefficients for example, a monolayer of oxygen adatoms on polycrystalline tungsten raises the ac for helium from 0.02 for a clean surface to 0.6. Roberts [388] and co-workers made use of this sensitivity to the presence of adsorbates to determine sticking probabilities for reactive gases on tungsten. West and Somorjai [389] have used the extent of He elastic scattering as a sensitive measure of surface cleanliness. 

That carbon monoxide could be oxidised in a facile reaction at cryogenic temperature (100 K) was first established in 1987 by XPS at an aluminium surface.21 The participation of reactive oxygen transients O 1 (s) was central to the mechanism proposed, whereas the chemisorbed oxide O2 state present at 295 K was unreactive. This provided a further impetus for the transient concept that was suggested for the mechanism of the oxidation of ammonia at a magnesium surface (see Chapter 2). Of particular relevance, and of crucial significance, was Ertl s observation by STM in 1992 that oxygen chemisorption at Al(lll) resulted in kinetically hot adatoms (Figures 4.1 and 4.7). 

Clearly the molecular events with iron were complex even at 80 K and low NO pressure, and in order to unravel details we chose to study NO adsorption on copper (42), a metal known to be considerably less reactive in chemisorption than iron. It was anticipated, by analogy with carbon monoxide, that nitric oxide would be molecularly adsorbed on copper at 80 K. This, however, was shown to be incorrect (43), and by contrast it was established that the molecule not only dissociated at 80 K, but NjO was generated catalytically within the adlayer. On warming the adlayer formed at 80 K to 295 K, the surface consisted entirely of chemisorbed oxygen with no evidence for nitrogen adatoms. It was the absence of nitrogen adatoms [with their characteristic N(ls) value] at both 80 and 295 K that misled us (43) initially to suggest that adsorption was entirely molecular at 80 K. 

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