Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 38, Pages 15882-15890Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c08153
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Funding
- National Key R&D Program of China [2017YFA0207302]
- National Natural Science Foundation of China [21890752, 21731005, 21721001]
- China Postdoctoral Science Foundation [2017M622076, 2021T140394, 2021M691877]
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A novel isomerization mechanism mediated by frustrated hydrogen atoms at defects on the solid surface was discovered, leading to a switch in selectivity from cis- to trans-configurations in olefins without overhydrogenation. The defective Rh2S3 with (110) facets exhibited outstanding performance as a catalyst for stereoselective production of trans-olefins. Bifunctional Rh-S/Pd nanosheets were synthesized through surface modification of Pd nanosheets, showing excellent activity and stereoselectivity in alkyne hydrogenation into trans-olefins.
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 H-2 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.
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