Origin of the superior hydrogenation selectivity of gold nanoparticles in alkyne + alkene mixtures: Triple- versus double-bond activation

DFT simulations have uncovered the origin of the highly selective character of gold nanoparticles in hydrogenation of triple bonds. This is ascribed to the better adsorption of C C at the edges of Au nanoparticles compared with C C. Since the barriers for hydrogenation of triple and double bonds on...

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Bibliographic Details
Published in:Journal of catalysis 2007-04, Vol.247 (2), p.383-386
Main Authors: Segura, Yolanda, López, Núria, Pérez-Ramírez, Javier
Format: Article
Language:English
Subjects:
Alkyne hydrogenation
Au/CeO 2
Catalysis
Catalytic cracking
Chemistry
Colloidal state and disperse state
DFT
Exact sciences and technology
General and physical chemistry
Gold
Gold nanoparticles
Hydrogenation
Hydrorefining
Nanoparticles
Palladium
Petrochemicals
Physical and chemical studies. Granulometry. Electrokinetic phenomena
Selectivity
Simulation
Steam cracking
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:DFT simulations have uncovered the origin of the highly selective character of gold nanoparticles in hydrogenation of triple bonds. This is ascribed to the better adsorption of C C at the edges of Au nanoparticles compared with C C. Since the barriers for hydrogenation of triple and double bonds on gold are comparable, selectivity is determined by the binding energy of the reactants. The situation is less favorable over palladium (commercial hydrorefining catalyst), because both C C and C C bonds are adsorbed on the Pd surface. The outcome of the simulations was demonstrated experimentally in mixtures with both propyne and propylene over a Au/CeO 2 catalyst, where C 3H 6 selectivities up to 95% were attained. Our finding opens a new path for chemoselective hydrogenation of molecules containing -yne and -ene groups on gold, with prospective application in petrochemical operations and in the fine chemical industry.
ISSN:0021-9517
1090-2694
DOI:10.1016/j.jcat.2007.02.019