Reactions of N and NO on Pt(335).
Tobin, Roger G.
DiMaggio, Craig L.
Fisher, Galen B.
Lambert, David K.
- As part of a study of species important in automotive exhaust chemistry, the reactivity of atomic N and NO on Pt(335) at low temperature has been studied. The atomic N was produced by dissociating adsorbed NO with a 76 eV electron beam. Cross sections for electron-stimulated desorption and dissociation are estimated for NO on terrace and step sites. Terrace NO is at least five times more likely to ... read moredesorb than to dissociate. Step NO has a lower desorption cross section than terrace NO, but probably a higher dissociation cross section. Temperature-programmed desorption was used to monitor desorption, dissociation, and the formation of N2N2 and N2ON2O from adsorbed N and NO. Five distinct desorption states of N2N2 formed by NO dissociation are identified. The dominant N2N2 peak (435 K) comes from electron-dissociated step NO; its desorption temperature is higher than the N2N2 peaks from electron-dissociated terrace NO. Coadsorbed N and NO react to form N2ON2O even below 100 K, with an activation barrier of ∼6 kcal/mol.∼6 kcal/mol. Only terrace NO participates in this reaction; step NO does not react to form N2O.N2O. This site dependence resembles that for CO oxidation on Pt(112) and Pt(335) and can be rationalized with simple steric considerations. All of the forms of atomic N participate in N2ON2O formation, but that formed by the dissociation of step NO exhibits the lowest reaction temperature. Hence, the same N atoms that only recombine to form N2N2 at 435 K, react with NO to form N2ON2O at 100 K. We found no evidence for an NO reaction with N atoms to form N2N2 and adsorbed O, or for NO formation from the recombination of adsorbed N and adsorbed O2.read less
- "Reactions of N and NO on Pt(335),"Hong Wang, R.G. Tobin, Craig L. DiMaggio, Galen B. Fisher, and David K. Lambert, J. Chem. Phys. 107, 9569 (1997). http://dx.doi.org/10.1063/1.475254.