Identifying Monomeric Fe Species for Efficient Direct Methane Oxidation to C1 Oxygenates with H2O2 over Fe/MOR Catalysts

Abstract

Exploring advanced catalysts and reaction systems operated at mild reaction conditions is crucial for conducting the direct methane oxidation reaction toward oxygenate products. Many efforts have been put into research on pentasil−type (MFI) zeolites based on mononuclear and/or binuclear iron sites, using H2O2 as the oxidant. In this work, we present a modified liquid ion−exchange method to better control Fe loading in a mordenite−type (MOR) zeolite with a Si/Al molar ratio of 9. The optimized Fe/MOR catalyst showed excellent performance in the direct methane oxidation reaction with turnover frequencies (TOFs) of 555 h−1 to C1 oxygenates, significantly better than the reported activity. Multiple comparative experiments were conducted to reveal the mechanism behind the performance. Strikingly, the active sites in the Fe/MOR catalyst were found to be mononuclear iron sites, confirmed by transmission electron microscopy (TEM), ultraviolet−visible diffuse reflectance spectroscopy (UV−vis DRS), and X-ray absorption spectroscopy (XAS). Increasing the iron loading led to the aggregation of the iron sites, which tend to trigger undesirable side reactions (i.e., H2O2 decomposition and over−oxidation), resulting in a significant decrease in TOFs to C1 oxygenates.