Engineering ZrO<sub>2</sub>-Ru interface to boost Fischer-Tropsch synthesis to olefins.

Yu, Hailing; Wang, Caiqi; Xin, Xin; Wei, Yao; Li, Shenggang; An, Yunlei; Sun, Fanfei; Lin, Tiejun et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Understanding the structures and reaction mechanisms of interfacial active sites in the Fisher-Tropsch synthesis reaction is highly desirable but challenging. Herein, we show that the ZrO<sub>2</sub>-Ru interface could be engineered by loading the ZrO<sub>2</sub> promoter onto silica-supported Ru nanoparticles (ZrRu/SiO<sub>2</sub>), achieving 7.6 times higher intrinsic activity and ~45% reduction in the apparent activation energy compared with the unpromoted Ru/SiO<sub>2</sub> catalyst. Various characterizations and theoretical calculations reveal that the highly dispersed ZrO<sub>2</sub> promoter strongly binds the Ru nanoparticles to form the Zr-O-Ru interfacial structure, which strengthens the hydrogen spillover effect and serves as a reservoir for active H species by forming Zr-OH* species. In particular, the formation of the Zr-O-Ru interface and presence of the hydroxyl species alter the H-assisted CO dissociation route from the formyl (HCO*) pathway to the hydroxy-methylidyne (COH*) pathway, significantly lowering the energy barrier of rate-limiting CO dissociation step and greatly increasing the reactivity. This investigation deepens our understanding of the metal-promoter interaction, and provides an effective strategy to design efficient industrial Fisher-Tropsch synthesis catalysts.