Surface structure effects in the adsorption and desorption of nitric oxide on rhodium

The adsorption, desorption and decomposition of NO on Rh surfaces have been investigated using field electron microscopy (FEM) and thermal desorption spectroscopy (TDS). At 77 K NO is molecularly adsorbed on all surfaces of Rh. At room temperature, however, about 30% of NO adsorbed on the rough surfaces is dissociated. The work function change Δφ due to NO adsorption increases as the surface becomes rougher. The results suggest the following order in Δφ: 0.93 eV = (100) < (111) < (511) < (410) < (331), (533) < (321) < (110) < (650) < (531), (210) = 1.4 eV. Upon heating the tip covered with molecular NO the FEM results suggest that the (321) surface is most active in the NO bond scission. The smooth surfaces are least effective in NO dissociation. The most likely interpretation of the FEM results is that the activity in NO bond scission increases in the following order: (111), (110) < (100), (511) < (650) < (410) < (210) < (331), (533) < (321). These results are discussed in relation to literature data concerning the dissociation of NO on the noble metals of Group VIII.