| Summary: | The types of supports employed profoundly influence the physicochemical properties and performances of as-prepared catalysts in almost all catalytic systems. Herein, Cu catalysts, with different supports (SiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>), were prepared by a facile impregnation method and used for the direct synthesis of higher alcohols from CO hydrogenation. The prepared catalysts were characterized using multiple techniques, such as X-ray diffraction (XRD), N<sub>2</sub> sorption, H<sub>2</sub>-temperature-programmed reduction (H<sub>2</sub>-TPR), temperature-programmed desorption of ammonia (NH<sub>3</sub>-TPD), X-ray photoelectron spectroscopy (XPS) and in situ Fourier-transform infrared spectroscopy (FTIR), etc. Compared to the Cu/Al<sub>2</sub>O<sub>3</sub> catalyst, the Cu/SiO<sub>2</sub> catalyst easily promoted the formation of a higher amount of C1 oxygenate species on the surface, which is closely related to the formation of higher alcohols. Simultaneously, the Cu/Al<sub>2</sub>O<sub>3</sub> and Cu/SiO<sub>2</sub> catalysts showed obvious differences in the CO conversion, alcohol distribution, and CO<sub>2</sub> selectivity, which were probably originated from differences in the structural and physicochemical properties, such as the types of copper species, the reduction behaviors, acidity, and electronic properties. Besides, it was also found that the gap in performances in two kinds of catalysts with the different supports could be narrowed by the addition of potassium because of its neutralization to surface acidy of Al<sub>2</sub>O<sub>3</sub> and the creation of new basic sites, as well as the alteration of electronic properties.
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