Adsorption dynamics of CO2 on Zn-ZnO(0001): a molecular beam study

Presented are initial S(0) and coverage Theta dependent, S(Theta), adsorption probability measurements, respectively, of CO(2) adsorption on the polar Zn-terminated surface of ZnO, parametric in the impact energy E(i), the surface temperature T(s), the impact angle alpha(i), varied along the [001] azimuth, the CO(2) flux, and the density of defects, chi(Ar(+)), as varied by rare gas ion sputtering. S(0) decreases linearly from 0.72 to 0.25 within E(i)=0.12-1.33 eV and is independent of T(s). Above E(i)=0.56 eV, S(0) decreases by approximately 0.2 with increasing alpha(i). The shape of S(Theta) curves is consistent with precursor-mediated adsorption (Kisliuk shape, i.e., S approximately const) for low E(i); above E(i)=0.56 eV, however, a turnover to adsorbate-assisted adsorption (S increases with Theta) has been observed. The initial slope of S(Theta) curves decreases thereby with increasing alpha(i), chi(Ar(+)), and T(s), i.e., the adsorbate-assisted adsorption is most distinct for normal impact on the pristine surface at low T(s) and is independent of the CO(2) flux. The S(Theta) curves have been parametrized by analytic precursor models and Monte Carlo simulations have been conducted as well. The temperature dependence of the saturation coverage shows two structures which could be assigned to adsorption on pristine and intrinsic defect sites, respectively, in agreement with a prior thermal desorption spectroscopy study. The heat of adsorption E(d) for the pristine sites amounts to 34.0-5.4Theta, whereas for adsorption on the intrinsic defect sites E(d) of approximately 43.6 kJ/mol could be estimated. Thus, a kinetic structure-activity relationship was present.