Selective hydrogenation of α,β-unsaturated ketones to α,β-unsaturated alcohols on gold-supported catalysts

Milone, Candida; Ingoglia, R.; Pistone, Alessandro; Neri, G.; Frusteri, F.; Galvagno, S.

doi:10.1016/j.jcat.2003.11.003

Cited by 115 publications

(31 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…12−14 For example, on the Au/Fe 2 O 3 catalyst, the hydrogenation selectivity to unsaturated alcohols was higher than 60% for benzalacetone and 4-methyl-3-penten-2-one but only 15% for the 3-penten-2-one. 12 In addition, Ide et al conducted experiments of selective hydrogenation of α,β-unsaturated ketones and aldehydes over various supported metal catalysts. 6 Rojas et al studied selective hydrogenation of benzalacetone over Au/SiO 2 and Ir/SiO 2 and found a selectivity of 46% to unsaturated alcohol on Au but a very low selectivity on Ir.…”

Section: ■ Introductionmentioning

confidence: 99%

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster

Ouyang

Jiang

2015

ACS Catal.

View full text Add to dashboard Cite

The Au 25 (SR) 18 cluster can catalyze 100% selective hydrogenation of α,β-unsaturated ketones to unsaturated alcohols. However, the mechanism remains a mystery. Here we unravel the underlying mechanism by using first-principles density functional theory calculations with benzalacetone as a substrate. We find that the Au 25 (SR) 18 cluster cannot directly activate either H 2 or benzalacetone separately. Instead, starting with coadsorption of H 2 and benzalacetone on Au 25 (SR) 18 , H 2 heterolytically cleaves to the substrate and to a surface Au atom of the cluster, followed by the facile transfer of H from the Au atom to the partially hydrogenated substrate. In this mechanism, CO and CC hydrogenations have barriers of 0.99 and 1.12 eV, respectively, in agreement with the experimentally observed selectivity toward unsaturated alcohol. In addition, we show that the ethanol solvent can further stabilize the partially hydrogenated intermediate of CO hydrogenation via a hydrogen bond, leading to a smaller H 2 cleavage energy (0.90 eV). Hence, the heterolytic cleavage of H 2 on the Au 25 nanocluster favors the more polar CO bond of benzalacetone, leading to selective formation of unsaturated alcohol. This work reveals that the weak interaction between H 2 and the Au cluster, the formation of a Au hydride, and the polar solvent are responsible for the high selectivity of the α,β-unsaturated ketone hydrogenation to the corresponding unsaturated alcohol over the Au 25 nanocluster.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster

Ouyang

Jiang

2015

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…[33,34] Gold is supported either on Fe2O3 or Al2O3, in different weight percentage and different particle size. Depending on the catalyst there is a differentiation in the selectivity during the hydrogenation of , -unsaturated ketones.…”

Section: The Case Of Ketonesmentioning

confidence: 99%

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Karaiskos¹,

Matiadis²,

Markopoulos³

et al. 2012

Hydrogenation

View full text Add to dashboard Cite

“…Supported nanostructured gold catalysts show a high selectivity towards hydrogenation of C=O bonds in the presence of double bonds during the conversion of unsaturated aldehyde or ketones to unsaturated alcohols. [19][20][21] However, studying the direct influence of the support on Au nanoparticles in binary versus ternary composites has, to the best of our knowledge, not been reported.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, the individual shape and morphology of the gold nanoparticles has an important influence on its catalytic activity and selectivity. [17][18][19][20][21] Au nanoparticles supported on TiO 2 , ZrO 2 , ZnO, Fe 2 O 3 and SiO 2 have been used for low-temperature CO oxidation, [18] hydrogenation [19][20][21] as well as for oxidation of hydrocarbons [18] and so forth. Supported nanostructured gold catalysts show a high selectivity towards hydrogenation of C=O bonds in the presence of double bonds during the conversion of unsaturated aldehyde or ketones to unsaturated alcohols.…”

Section: Introductionmentioning

confidence: 99%

Binary Au/MWCNT and Ternary Au/ZnO/MWCNT Nanocomposites: Synthesis, Characterisation and Catalytic Performance

Hoffmann

Engstler

Schneider

et al. 2010

Chemistry A European J

View full text Add to dashboard Cite

Gold nanoparticles of 10-24 and 5-8 nm in size were obtained by chemical citrate reduction and UV photoreduction, respectively, on acid-treated multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNT composites. The shape and size of the deposited Au nanoparticles were found to be dependent upon the synthetic method used. Single-crystalline, hexagonal gold particles were produced in the case of UV photoreduction on ZnO/MWCNT, whereas spherical Au particles were deposited on MWCNT when the chemical citrate reduction method was used. In the UV photoreduction route, n-doped ZnO serves as the e(-) donor, whereas the solvent is the hole trap. All materials were fully characterised by UV/Vis spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and BET surface analysis. The catalytic activity of the composites was studied for the selective hydrogenation of alpha,beta-unsaturated carbonyl compound 3,7-dimethyl-2,6-octadienal (citral). The Au/ZnO/MWCNT composite favours the formation of unsaturated alcohols (selectivity=50% at a citral conversion of 20%) due to the presence of single-crystalline, hexagonal gold particles, whereas saturated aldehyde formation is favoured in the case of the Au/MWCNT nanocomposite that contains spherical gold particles.

show abstract

Selective hydrogenation of α,β-unsaturated ketones to α,β-unsaturated alcohols on gold-supported catalysts

Cited by 115 publications

References 19 publications

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Binary Au/MWCNT and Ternary Au/ZnO/MWCNT Nanocomposites: Synthesis, Characterisation and Catalytic Performance

Contact Info

Product

Resources

About

Selective hydrogenation of α,β-unsaturated ketones to α,β-unsaturated alcohols on gold-supported catalysts

Cited by 115 publications

References 19 publications

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au25(SR)18 Cluster

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au25(SR)18 Cluster

Homogeneous Chemoselective Hydrogenation of Heterocyclic Compounds – The Case of 1,4 Addition on Conjugated C-C and C-O Double Bonds of Arylidene Tetramic Acids

Binary Au/MWCNT and Ternary Au/ZnO/MWCNT Nanocomposites: Synthesis, Characterisation and Catalytic Performance

Contact Info

Product

Resources

About

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster

Understanding Selective Hydrogenation of α,β-Unsaturated Ketones to Unsaturated Alcohols on the Au₂₅(SR)₁₈ Cluster