화학공학소재연구정보센터
Langmuir, Vol.29, No.1, 168-174, 2013
Interactions of NO2 with Zr-Based MOF: Effects of the Size of Organic Linkers on NO2 Adsorption at Ambient Conditions
Zirconium-based metal organic framework (Zr-MOF), UiO-66 and UiO-67, were synthesized and used as adsorbents of NO2 at ambient temperatures in either dry or moist conditions. The samples were characterized before and after exposure to NO2 by X-ray diffraction, scanning electron microscopy, N-2- adsorption at 77 K, thermal analysis, and infrared spectroscopy. The results indicate the important effect of a ligand size on the adsorption of NO2 on Zr-MOF materials. While the large size of the 4,4-benzenebiphenyldicarboxylic acid (BDPC) ligand has a positive impact on the adsorption of NO2 on UiO-67 in moist conditions, the opposite effect is found in dry conditions. The large pore volume of UiO-67 enhances the adsorption of moisture and formation of nitric and nitrous acids. The small pore sizes of UiO-66 favor the NO2 removal in dry conditions via dispersive forces. Upon interaction of NO2 molecules with the Zr-MOF in dry conditions, the bond between the organic linker and metallic oxide center is broken, leading to the formation of nitrate and nitrite species. Moreover, organic ligands also contribute to the NO2 reactive adsorption via nitration reaction.