Reference : Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorpti...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/10993/25681
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
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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 mailto [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]
2014
Journal of Physical Chemistry. C, Nanomaterials and interfaces
AMER CHEMICAL SOC
118
48
27833-27842
Yes (verified by ORBilu)
International
1932-7447
1155 16TH ST, NW, WASHINGTON, DC 20036 USA
[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).
http://hdl.handle.net/10993/25681
10.1021/jp506637v
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