A mechanistic insight into rhodium-doped gold clusters as a better hydrogenation catalyst
Turbasu Sengupta1, Jin Suk Chung1, Sung Gu Kang1
1School of Chemical Engineering, University of Ulsan, 93 Daehakro, Nam-Gu, Ulsan 44610, South Korea. jschung@mail.ulsan.ac.kr sgkang@mail.ulsan.ac.kr.
Abstract:
The reaction mechanism of the hydrogenation of ethylene on pristine (Aun, n = 8 and 20) and rhodium-doped (AunRh) gold clusters was unveiled by theoretical calculations. All reaction pathways are predicted and the thermodynamic and kinetic parameters are computed and compared. Doping a rhodium atom on the magic gold cluster surface is effective in reducing the activation barriers for hydrogenation and in creating two competitive pathways with significantly higher turnover frequencies. The lower barriers of hydrogenation on the AunRh clusters were analyzed and explained based on distortion/interaction activation strain (DIAS) analysis. Further insights into the reaction mechanism on both types of clusters are provided by intrinsic bond orbital (IBO) calculations. This theoretical study provides an idea to elucidate the hydrogenation mechanism on Au clusters and the effect of the rhodium dopant on the catalytic process.
More Related Videos
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Related Concept Videos
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Catalysis
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
