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Spectators Control Selectivity in Surface Chemistry: Acrolein Partial Hydrogenation Over Pd

MPS-Authors
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Dostert,  Karl-Heinz
Chemical Physics, Fritz Haber Institute, Max Planck Society;

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O'Brien,  Casey P.
Chemical Physics, Fritz Haber Institute, Max Planck Society;

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Ivars Barcelo,  Francisco
Chemical Physics, Fritz Haber Institute, Max Planck Society;

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Schauermann,  Swetlana
Chemical Physics, Fritz Haber Institute, Max Planck Society;
Physikalische Chemie, Christian-Albrechts-Universität zu Kiel;

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Freund,  Hans-Joachim
Chemical Physics, Fritz Haber Institute, Max Planck Society;

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ja5b04363 1..7 - jacs.pdf
(Publisher version), 2MB

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Citation

Dostert, K.-H., O'Brien, C. P., Ivars Barcelo, F., Schauermann, S., & Freund, H.-J. (2015). Spectators Control Selectivity in Surface Chemistry: Acrolein Partial Hydrogenation Over Pd. Journal of the American Chemical Society, 137(42), 13496-13502. doi:10.1021/jacs.5b04363.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0029-0AEF-8
Abstract
We present a mechanistic study on selective hydrogenation of acrolein over model Pd surfaces—both single crystal Pd(111) and Pd nanoparticles supported on a model oxide support. We show for the first time that selective hydrogenation of the C═O bond in acrolein to form an unsaturated alcohol is possible over Pd(111) with nearly 100% selectivity. However, this process requires a very distinct modification of the Pd(111) surface with an overlayer of oxopropyl spectator species that are formed from acrolein during the initial stages of reaction and turn the metal surface selective toward propenol formation. By applying pulsed multimolecular beam experiments and in situ infrared reflection–absorption spectroscopy, we identified the chemical nature of the spectator and the reactive surface intermediate (propenoxy species) and experimentally followed the simultaneous evolution of the reactive intermediate on the surface and formation of the product in the gas phase.