Article (Scientific journals)
Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies
Dostert, Karl-Heinz; O'Brien, Casey P.; Riedel, Wiebke et al.
2014In Journal of Physical Chemistry. C, Nanomaterials and interfaces, 118 (48), p. 27833-27842
Peer reviewed
 

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Interaction of Isophorone with Pd(111): A Combination of Infrared Re fl ection − Absorption Spectroscopy, Near-Edge X ‑ ray Absorption Fine Structure, and Density Functional Theory Studies.pdf
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Abstract :
[en] Atomistic level understanding of interaction of alpha,beta-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C-C or C-O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on alpha,beta-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflectionabsorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C-C and C-O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C-C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated p system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both p bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated pi system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111).
Disciplines :
Chemistry
Author, co-author :
Dostert, Karl-Heinz;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
O'Brien, Casey P.;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Riedel, Wiebke;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Aditya, Savara;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Liu, Wei;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Oehzelt, Martin;  Helmholtz-Zentrum fu r Materialien und Energie, Albert-Einstein-Straße 15, 12489 Berlin, Germany
Tkatchenko, Alexandre ;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
Schauermann, Swetlana;  Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
External co-authors :
yes
Title :
Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies
Publication date :
2014
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
ISSN :
1932-7447
Publisher :
AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA, Unknown/unspecified
Volume :
118
Issue :
48
Pages :
27833-27842
Peer reviewed :
Peer reviewed
Commentary :
Article
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