Microcalorimetry of O2 and NO on flat and stepped platinum surfaces

Using the single-crystal adsorption calorimeter (SCAC), coverage-dependent heats of adsorption and sticking probabilities are reported for O2 and NO on Pt{1 1 1}, Pt{2 1 1} and Pt{4 1 1} at 300 K. At low coverage, oxygen adsorption is dissociative for all Pt surfaces. The highest initial heat of adsorption is found on Pt{2 1 1}, with a value of 370 kJ/mol, followed by those on Pt{4 1 1} (310 kJ/mol) and Pt{1 1 1} (300 kJ/mol). We attribute this relatively large difference in the dissociative heat of adsorption at low coverage to the step character of the {2 1 1} surface. Initial sticking probabilities, so, are similar for the three surfaces, 0.22 on Pt{1 1 1}, 0.17 on Pt{2 1 1} and 0.18 on Pt{4 1 1}, rapidly decreasing as the oxygen coverage increases. For nitric oxide, the initial heats of adsorption are very similar and consistent with either dissociative or molecular adsorption, with values of 182 kJ/mol on Pt{1 1 1}, 192 kJ/mol on Pt{2 1 1} and 217 kJ/mol on Pt{4 1 1}. The so value is virtually identical for all three systems, with values ranging from 0.82 to 0.85, suggesting that the initial sticking probability is insensitive to the surface structure and adsorption is intrinsically precursor mediated. SCAC data are also used to evaluate pre-exponential factors, ν, for first-order desorption at high coverage where adsorption is non-dissociative. Values of 3 × 1018, 6 × 1018 and 2 × 1018 s−1 for O2, and 4 × 1019, 6 × 1017 and 2 × 1020 s−1 for NO on Pt{1 1 1}, Pt{2 1 1} and Pt{4 1 1}, respectively, are found. These unexpectedly high values are rationalised in terms of conventional transition state theory entropy changes.