Catalytic Interplay of Ga, Pt, and Ce on the Alumina Surface Enabling High Activity, Selectivity, and Stability in Propane Dehydrogenation

Pt-based bimetallic catalysts have been widely investigated in propane dehydrogenation (PDH) owing to their high activity in C–H cleavage and propylene selectivity. However, upon repeated coke oxidation for catalyst regeneration, they suffer from significant metal sintering and dealloying. Recently, γ-Al₂O₃ doped with Ga, Pt, and Ce was reported to exhibit superior catalytic activity, selectivity, and stability in PDH, but the catalytic role of each element has not been clearly understood because of the complexity of this system. In this study, we rigorously investigated the reaction mechanism and catalytic interplay of each component (Ga, Pt, and Ce). Selective poisoning, in situ diffuse reflectance infrared Fourier transform spectroscopy, and H₂–D₂ exchange revealed that Ga³⁺ is responsible for the heterolytic dissociation of the C–H bond of propane, while Pt⁰ facilitates the sluggish H recombination into H₂ via reverse spillover. Catalyst deactivation during repeated reaction–regeneration cycles is mainly due to the irreversible sintering of Pt⁰. Notably, optimal Ce doping (∼2 wt %) selectively generated atomically dispersed Ce³⁺ sites on the γ-Al₂O₃ surface, which greatly suppressed the sintering of Pt⁰ particles by increasing the metal–support interactions. In contrast, excessive Ce loading generated discrete CeO₂ domains, which stabilized the Pt species in the form of Pt²⁺ inactive for H recombination. Thus, excessive Ce loading led to an even more severe loss of catalytic activity and selectivity. The present results demonstrate that the selective generation of atomically dispersed Ce³⁺ on the γ-Al₂O₃ surface is important for stabilizing Pt⁰ species, which is essential for simultaneously achieving high catalytic activity, selectivity, and longevity in PDH.