The influence of steps on the dissociation of NO on Pt surfaces: Temperature-programmed desorption studies of NO adsorption on Pt{211}

Temperature-programmed desorption (TPD) has been used to investigate the adsorption of NO on Pt{211} at 300 K and 120 K. Results show that NO dissociation occurs readily on Pt{211}, as evidenced by the observation of N2 and N2O in the TPD spectrum. Following adsorption at 120 K three NO TPD peaks at 338, 416, and 503 K are observed, in agreement with previous observations. In combination with data acquired in a recent reflection absorption infrared spectroscopy and density functional theory investigation of NO/Pt{211}, these peaks are assigned to the desorption of NO from an O–NO complex, the recombinative desorption of N and O atoms, and to desorption of a step-bridged NO species, respectively. These assignments are in disagreement with previous work, where the high-temperature NO peak was assigned to the desorption of step bound NO and the two low-temperature peaks were assigned to the desorption of NO from terrace sites. TPD spectra recorded following adsorption at 300 K, with a heating rate of 1 K s−1, show similar features to those recorded following 120 K adsorption. This is also in disagreement with previous observations, where only two NO TPD peaks were observed following adsorption at room temperature. This disagreement can be accounted for by the different heating rates used in the two experiments.