Título:
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Concerted Chemoselective Hydrogenation of Acrolein on Secondary Phosphine Oxide Decorated Gold Nanoparticles
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Autor/a:
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Almora-Barrios, Neyvis; Cano, Israel; van Leeuwen, Piet W. N. M.; López, Núria
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Abstract:
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Secondary phosphine oxides (SPOs) can be used as ligands to
stabilize catalytically active gold nanoparticles (AuNPs). These materials are
active and very selective in the chemoselective hydrogenation of acrolein and
other α,β-unsaturated aldehydes, but the origin of the activity remains elusive.
Here, by means of density functional theory, we identify a cooperative effect at
the AuNP−SPO interface that enables the heterolytic cleavage of the H2
molecule and its kinetically favorable concerted addition to the CO bond
(in a transfer hydrogenation-like mode) to form the corresponding allyl alcohol.
From the mechanism it is possible to identify the descriptors that explain the
activity for a family of SPO-stabilized AuNPs and a set of unsaturated aldehydes.
The activity depends on the basicity difference between ligand and reactant and
the sites available on the nanoparticle. |
Fecha de creación:
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26-04-2017 |
Materia(s):
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54 |
Derechos:
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L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/ |
Páginas:
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3949 p. |
Tipo de documento:
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Artículo Artículo - Versión aceptada |
DOI:
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10.1021/acscatal.7b00355c
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