Atomic-Scale Dynamics of Surface-Catalyzed Hydrogenation/Dehydrogenation: NH on Pt(111)

Low-temperature scanning tunneling microscopy (LT-STM) was used to move hydrogen atoms and dissociate NH molecules on a Pt(111) surface covered with an ordered array of nitrogen atoms in a (2 x 2) structure. The N-covered Pt(111) surface was prepared by ammonia oxydehydrogenation, which was achieved by annealing an ammonia-oxygen overlayer to 400 K. Exposing the N-covered surface to H-2(g) forms H atoms and NH molecules. The NH molecules occupy face-centered cubic hollow sites, while the H atoms occupy atop sites. The STM tip was used to dissociate NH and to induce hopping of H atoms. Action spectra consisting of the reaction yield versus applied bias voltage were recorded for both processes, which revealed that they are vibrationally mediated. The threshold voltages for NH dissociation and H hopping were found to be 430 and 272 meV, corresponding to the excitation energy of the N-H stretching and the Pt-H stretching modes, respectively. Substituting H with D results in an isotopic shift of -110 and -84 meV for the threshold voltages for ND dissociation and D hopping, respectively. This further supports the conclusion that these processes are vibrationally mediated.