Low-Temperature Oxidative Dehydrogenation of n-Butene over Oleate-Mediated ZnFe2O4 Catalysts

Traditional oxidative dehydrogenation of n-butene has typically required relatively high operating temperatures (400–500 °C), which has driven increasing interest in the development of catalysts capable of delivering high activity at lower temperatures. In this study, zinc ferrite (ZnFe2O4-ST) was successfully synthesized via hydrothermal hydrolysis of Zn–Fe oleate and demonstrated remarkable catalytic performance for the oxidative dehydrogenation of n-butene under mild conditions. At 300 °C, ZnFe2O4-ST achieved a conversion of 72.9% with 92.1% selectivity toward 1,3-butadiene, a result that, to the best of our knowledge, ranks among the best reported in the literature. By contrast, ZnFe2O4 prepared by conventional coprecipitation (17.2% conversion with 91.3% selectivity) and sol-gel (10.1% conversion with 86.4% selectivity) methods showed much lower activities, highlighting the critical influence of synthesis strategy on catalytic performance. To better understand the origin of these differences, a detailed structural and physicochemical characterization was undertaken using X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), N2 adsorption–desorption, X-ray photoelectron spectroscopy (XPS), H2-temperature-programmed reduction (H2-TPR), temperature-programmed re-oxidation (TPRO), and NH3-temperature-programmed desorption (NH3-TPD). These analyses revealed that the as-synthesized ZnFe2O4-ST possessed a significantly smaller average particle size, a larger specific surface area, and superior reducibility compared with the other samples. These properties are believed to be the key factors underpinning its outstanding catalytic behavior and provide important insights into the design of efficient low-temperature catalysts for selective oxidative dehydrogenation.