Insights into the Nature of Selective Nickel Sites on Ni/Al2O3 Catalysts for Propane Dehydrogenation

Nickel has been considered a promising nonprecious metal for propane dehydrogenation (PDH) because of its appealing ability to activate alkane molecules; however, synthesis of selective and stable Ni sites remains a challenge. Herein, we describe an alumina-supported isolated Ni(II) site by settling Ni2+ cations into Al3+ vacancy on γ-Al2O3 as a selective and stable Ni-based catalyst for PDH. Based on the results from combined characterizations, including in situ X-ray adsorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), atomically dispersed Ni(II) sites with bonding to oxygen ions from the alumina support are demonstrated. PDH catalyst tests shows that the Ni(II) single-site catalyst delivers superior performance compared to a supported metallic Ni NP catalyst, possessing >93% propylene selectivity at considerable propane conversions (15–45%), which surpasses Ni nanoparticle (NP) catalysts. The correlation of selectivity to propylene on different Ni structures with the structural characterizations suggest that the coordinatively unsaturated tetrahedral Ni(II) sites facilitate the desorption of propylene, which inhibits the side reactions for coking. Moreover, the atomically dispersed Ni(II) sites remain in its local structure in the reaction-regeneration cycles, as evidenced by in situ XAS. This study on alumina-supported nickel catalysts affords insights into the nature of selective and stable nickel sites involved in the PDH reaction.