[JACS] 我室郑南峰教授发表论文:Heterogeneous Isomerization for Stereoselective Alkyne Hydrogenation to trans-Alkene Mediated by Frustrated Hydrogen Atoms

发布日期:2021年10月08日   浏览次数:

我室郑南峰教授在 JACS 上发表论文:Heterogeneous Isomerization for Stereoselective Alkyne Hydrogenation to trans-Alkene Mediated by Frustrated Hydrogen Atoms

摘要:Stereoselective production of alkenes from the alkyne hydrogenation plays a crucial role in the chemical industry. However, for heterogeneous metal catalysts, the olefins in cis-configuration are usually dominant in the products due to the most important and common Horiuti–Polanyi mechanism involved over the metal surface. In this work, through combined theoretical and experimental investigations, we demonstrate a novel isomerization mechanism mediated by the frustrated hydrogen atoms via the H2 dissociation at the defect on solid surface, which can lead to the switch in selectivity from the cis-configuration to trans-configuration without overhydrogenation. The defective Rh2S3 with exposing facet of (110) exhibits outstanding performance as a heterogeneous metal catalyst for stereoselective production of trans-olefins. With the frustrated hydrogen atoms at spatially separated high-valence Rh sites, the isolated hydrogen mediated cis-to-trans isomerization of olefins can be effectively conducted and the overhydrogenation can be completely inhibited. Furthermore, the bifunctional Rh–S/Pd nanosheets have been synthesized through the surface modification of Pd nanosheets with rhodium and sulfide. With the selective semihydrogenation of alkynes into cis-olefins catalyzed by the small surface PdSx ensembles, the bifunctional Rh–S/Pd nanosheets exhibit excellent activity and stereoselectivity in the one-pot alkyne hydrogenation into trans-olefin, which surpasses the most reported homogeneous and heterogeneous catalysts.

文章链接:https://pubs.acs.org/doi/10.1021/jacs.1c08153