Qualitative Differences in the Adsorption Chemistry of Acidic (CO₂, SO_x) and Amphiphilic (NO_x) Species on the Alkaline Earth Oxides

Density functional theory calculations and plane-wave, supercell models are used to examine trends in the adsorption chemistry of CO₂, SO_x (x = 1, 2), and NO_x (x = 1, 2, 3) on the (001) surfaces of the alkaline earth oxides MgO through BaO. The Lewis acids CO₂ and SO_x adsorb at basic surface oxygen (O_s^2-) sites to form local carbonate (CO₃^2-)-, sulfite (SO₃^2-)-, and sulfate (SO₄^2-)-like structures, with adsorption energies increasing uniformly down the series. In contrast, the most stable NO_x-derived anions (nitrite, NO₂^-, and nitrate, NO₃^-) are not formed by Lewis acid−base reactions with acidic (M_s²⁺) or basic metal oxide surface sites alone. Rather, NO_x adsorption involves both electron transfer and acid−base interactions with the oxide surface that combine to produce acid-like and base-like adsorption states; the increasing oxidizability and reducibility of the alkaline earth oxides contribute to the increasing NO_x adsorption strength down the family. Combining NO_x adsorbates in acidic donor and basic acceptor configurations produces structural modifications and systematically enhanced adsorption energies that arise from interadsorbate charge transfer. These “cooperative” pairs provide qualitatively correct representations of chemisorbed nitrite and nitrate, and comparisons with available experiment support their utility for quantitative description of adsorption energetics as well. The electron transfer and cooperative interactions that distinguish NO_x from SO_x and CO₂ can potentially be exploited to tailor materials selective for NO_x adsorptionan important goal for NO_x emissions control.