Transformation of Propane over ZnSnPt Modified Defective HZSM-5 Zeolites: The Crucial Role of Hydroxyl Nests Concentration

Abstract

A series of ZnSnPt supported defective MFI zeolites with different SiO2/Al2O3 ratios (30, 110, 700, and ∞) and hydroxyl nests concentration were prepared and characterized by multiple techniques including scanning electron microscopy (SEM), nitrogen physisorption, NH3-TPD, transmission electron microscopy (TEM), hydrogen temperature programmed reduction (H2-TPR), and Fourier transform infrared spectrometer (FT-IR). It was found that Brønsted acid sites (Si(OH)Al) with strong acid strength and the hydroxyl nests with weak acid strength coexisted over the defective ZSM-5 zeolites and ZnSnPt Lewis acid sites preferentially located on the hydroxyl nests. The increase in the concentration of hydroxyl nests and SiO2/Al2O3 ratios apparently improved the distribution of ZnSnPt Lewis acid sites. The hydroxyl nest incorporated ZnSnPt Lewis acid sites showed extraordinary dehydrogenation ability. Specially, operando dual beam Fourier transform infrared spectrometer (DB-FTIR) was applied to characterize the propane transformation under reaction conditions. At low SiO2/Al2O3 ratios, the propane efficiently transforms into propene and aromatics (total selectivity of 93.37%) by the cooperation of Brønsted acid sites and ZnSnPt Lewis acid sites. While at high SiO2/Al2O3 ratios, the propane mainly transforms into propene (selectivity of above 95%) and hydrogen. This study provides guidance for the preparation of highly efficient propane dehydrogenative transformation catalyst.