Journal of Physical Chemistry B, Vol.105, No.18, 3724-3732, 2001
N-2 chemisorption on stepped Pt surfaces. Control by 2-D and 1-D precursor behavior
Nitrogen adsorption uptake at 88 K and temperature-programmed desorption (TPD) experiments were done on two stepped platinum surfaces, Pt(335) and Pt(779). N-2 adsorption occurs only on the step sites, and the saturation coverages measured on these surfaces were (1.51 +/- 0.09) x 10(14) and (1.01 +/- 0.16) x 10(14) cm(-2), respectively, indicating a higher fractional population of widely separated step sites compared to closely spaced step sites. The adsorption kinetics revealed that the adsorption is mediated by terrace and step precursors. The N-2 initial sticking probability is 0.91 +/- 0.06 (average of six measurements) on the Pt(335) surface and 0.68 +/- 0.07 (average of five measurements) on the Pt(779) surface. The binding energy of N-2 at step sites, determined from experimental and simulated TPD curves, is -0.50 eV at zero coverage and decreases monotonically to -0.44 eV at saturation coverage on both surfaces. The equilibrium thermodynamics of N-2 adsorbed on either of the two stepped Pt surfaces are the same. The role of terrace width on the initial sticking probability is discussed for adsorption on stepped surfaces.