Abstraction of D adsorbed on Pt(111) surfaces with gaseous H atoms

The impact of gaseous H atoms at D covered Pt(111) surfaces at 85 K leads to the formation of gaseous HD and D-2 products. The kinetics of formation of these products was measured simultaneously with H exposure for different initial D coverages. The HD and D-2 rates as a function of H fluence from the reaction start exhibit common characteristics; a rate step, a rate maximum, and a subsequent exponential rate decay. The HD and D-2 rate steps were observed not to scale linear with the D coverage and to increase if on D covered surfaces H was coadsorbed prior to reaction. Of the observed phenomena, only the exponential decay of the HD rate is in line with expectations if an Eley-Rideal mechanism acts in the present reaction. D2 formation, the HD rate step as a function of D coverage, and the presence of a H coadsorbate contradict the Eley-Rideal picture. The results suggest that the reactions towards HD and D-2 proceed via hot atom type mechanisms. (C) 1998 American Institute of Physics.