In this study, the dissociative adsorption of NaNO2, NaNO3, HNO2, HNO3 and H2SO4 over (1 1 0) surface of γ-alumina non-spinel model were investigated through the dispersion corrected density functional theory (DFT-D) at PBE-D/DNP level of calculation. It was found that all of the species are dissociated to their ionic forms after adsorption and relaxation over the surface, i.e. Na+NO2−, Na+NO3−, H+NO2−, H+NO3−, H+HSO4− and 2H+SO42−. The Lewis acidity of alumina surface by addition of HNO2, HNO3 and H2SO4 is increased, while in the presence of NaNO2 and NaNO3, the acidity of catalyst is decreased. Theoretical calculations predict stronger dissociative adsorption of H2SO4 over the surface in compared to other compounds. The HNO2 and HNO3 mineral acids are better adsorbed over the surface than NaNO2 and NaNO3 salts. The better adsorption of nitrites than nitrates is due to the stronger electrostatic attractions. The order of NaNO3 < NaNO2 < HNO3 < HNO2 < H2SO4 for the dissociative adsorption energy of the title compounds is predicted. تفاصيل المقالة

The influence of NaNO2, HNO3 and H2SO4 on the structure and morphology of gamma-alumina was investigated by XRD, BET, SEM and FT-IR spectroscopy. Selected amounts of NaNO2, HNO3 and H2SO4 were added to a solution of aluminum isopropoxide (as a precursor for the boehmite synthesis). The boehmite samples were calcined at 350 and 600 ℃ to form the semi-crystalline high surface area gamma-Al2O3. The reactivity and selectivity of the modified gamma-alumina catalysts were examined using dehydration reaction of 2-octanol. There was a good correlation between reactivity, selectivity and the amounts (and type) of the modification. The dominant product was cis-2-octene for all of the catalysts. Low conversion and high selectivity were obtained for dehydration of 2-octanol over alumina modified with NaNO2. High conversion, low selectivity and excessive isomerization were found for gamma-alumina catalyst modified with H2SO4. تفاصيل المقالة