Journal Article

Engineering ZrO 2 -Ru interface to boost Fischer-Tropsch synthesis to olefins

Sun, Fanfei, An, Yunlei, Wang, Caiqi, Yu, Hailing, Xin, Xin, Li, Shenggang, Wei, Yao, Lin, Tiejun, Zhong, Liangshu

2024

Overview

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 -Ru interface could be engineered by loading the ZrO promoter onto silica-supported Ru nanoparticles (ZrRu/SiO ), achieving 7.6 times higher intrinsic activity and ~45% reduction in the apparent activation energy compared with the unpromoted Ru/SiO catalyst. Various characterizations and theoretical calculations reveal that the highly dispersed ZrO 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.