Interactions of NO2 with Amine-Functionalized SBA-15: Effects of Synthesis Route

SBA-15 mesoporous silica was modified using (3-aminopropyl)trimethoxysilane (APTMS) following co-condensation or grafting methods and then used as a NO2 adsorbent at room temperature. The samples were characterized before and after exposure to NO2 by SEM-EDX, N-2 adsorption at 77 K, potentiometric titration, thermal analysis, and FTIR spectroscopy. Even though, regardless of the synthesis route, the addition of propylamine groups leads to a significant enhancement in the amount of NO2 adsorbed (from 21 to 124 mg(NO2)/g), a higher retention of NO2 and NO (released as a result of surface reactions) was measured on the grafted silica than on all of the co-condensed samples. In the case of the latter materials, improvements in both NO2 adsorption capacity and NO retention were found for the samples treated with NaOH. This behavior is related to the higher reactivity of deprotonated propylamine groups (formed during NaOH treatment) with NO2, the presence of silanol groups, and the residual amount of sodium present in the samples. The mechanism of NO2 adsorption on propylamine groups involves the formation of nitramine and/or nitrosamine. Analysis of the spent materials indicates that the porosity of co-condensed materials is not affected to the same extent by adsorption of NO2 as that of the grafted silica.