Effects of surface acidities of MCM-41 modified with MoO3 on adsorptive desulfurization of gasoline

A series of MCM-41 samples containing molybdenum oxide as active species in the mesoporous channels loaded by spontaneous monolayer dispersion (SMD) and impregnation (IM) have been prepared and characterized using XRD, N2 adsorption-desorption analysis, Fourier transform infrared spectroscopy (FTIR) and intelligent gravimetric analyzer (IGA). The relative number of hydroxy on the adsorbents was investigated by in situ FTIR. Surface acidities of the adsorbents were studied by infrared spectroscopy of adsorbed pyridine and correlated with reactivity for adsorptive desulfurization. The IGA technique was employed to investigate adsorption behavior of thiophene and benzene on the adsorbents at 303 K. It is shown that MoO3 can be highly dispersed up to 0.2 g g−1 in the MCM-41 channels by the SMD strategy with the ordered mesoporous structure of the MoMM samples remaining intact. The ordered mesostructure of MCM-41 is, however, destroyed at higher MoO3 contents of 0.26 and 0.32 g g−1 with particle sizes of 1.2 nm and 3.6 nm, respectively, observed. For the MoMI(0.2) sample prepared by the IM method, the aggregation of the MoO3 particles takes place with a particle size of 6.5 nm obtained. The results are also revealed that the dispersion extent of the MoO3 species is related to the abundant surface hydroxy of MCM-41. The host species and guest species undergo solid-state reaction to form SiOMo bonds in the mixtures which enhance both the Lewis acid and Brönsted acid of the samples. It has been concluded that the surface acidities of the sorbents contributes to the desulfurization performance which has also been investigated in this study. The octahedral coordinated species (Mo7O246−) are the adsorptive active species for desulfurization compared with the tetrahedral coordinated ones (MoO42−).

► The MoO3-MCM-41 samples prepared by spontaneous monolayer dispersion and impregnation with a different MoO3 filling have been studied. ► The relative concentration of hydroxyl groups present on before and after containing MoO3 samples was monitored by in situ FTIR to speculate the bonding style of MoO3 and MCM-41. ► The surface acidities of the MoO3-MCM-41 adsorbents were investigated systematically and correlated with the desulfurization performance.