Real-time observation of coadsorption layers on Ru(001) using a temperature-programmed ESDIAD/TOF system

For the purpose of utilizing ESDIAD as a real-time probe for surface processes, we have developed an instrument which can measure ESDIAD images and time of flight (TOF) spectra of desorbing ions in temperature-programmed surface processes. TOF measurements are carried out to identify the mass and to determine the kinetic energy distribution of the desorbed ions. This temperature-programmed (TP-) ESDIAD/TOF system was used to observe coadsorption layers of methylamine and CO on Ru(001) which have been previously studied by our group using LEED, TPD and HREELS, also drawing upon a comparison of findings with the coadsorption system of CO and ammonia. ESDIAD images acquired for temperature-programmed surface processes in real time were found to provide new insight into the dynamic behaviour of the coadsorption layers. As to the pure adsorption of ammonia and methylamine, the second and the first (chemisorbed) layers can be easily discriminated in their different ESD detection efficiency due to the difference in neutralization rate. The intensity change of H⁺ ions with temperature shows the process of the decomposition of methylamine to be dependent on CO coverage. The intensity of O⁺ originating from CO changes due to the change of CO adsorption site in the reaction process. The angular distribution of H⁺ ions which correspond to CH2=NH…Ru species appears at 250–300 K in the presence of high CO pre-coverage.     

Crystallographic study of interaction between adspecies on metal surfaces

The interaction among adsorbed atoms and molecules (adspecies) on metal surfaces plays a decisive role in catalytic reactions. Such interaction may cause structural changes of the local adsorption geometry which, together with spectroscopic and energetic data, may afford useful physical and chemical insights into the basic mechanisms of surface processes. When the adsorption geometry of a single adspecies is considered as a function of coverage, a deeper understanding of the nature of the adsorbate-substrate bonding can be obtained. Depending on the adsorbate coverage, the magnitude of adsorbate-induced relaxations and reconstructions vary widely. Occasionally, chemisorption systems transform gradually into adsorbate-substrate compounds, such as oxides, nitrides, hydrides, and sulfides. For the case of adsorption of different adspecies, coadsorption, structural data can make a vital contribution to our understanding of reaction intermediates, the promotion effect in heterogeneously catalyzed reactions, and the formation of ultra-thin compound films.     

Kinetic energy distributions and momentum resolved ESDIAD measurements of CO ions and excited neutral CO* molecules — CO/Cu(110)

We report for the first time a coincidence of the kinetic energy distributions of the ionic and excited neutral forms of a desorbing species produced by electron impact. By using a novel TOF-ESDIAD instrument and applying different accelerating voltages between the sample and the detector it was possible to separate CO⁺ from neutral CO* species by their flight times and to perform momentum-resolved ESDIAD measurements of the O⁺, CO⁺ and neutral CO* species. Two possible desorption scenarios are discussed.