Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Lee Durndell, Christopher M.A. Parlett, Nicole S. Hondow, Mark A. Issacs, Karen Wilson, Adam Lee*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

Original languageEnglish
Article number9425
Pages (from-to)1-9
Number of pages9
JournalScientific Reports
Volume5
DOIs
Publication statusPublished - 24 Mar 2015

Bibliographical note

This work is licensed under a Creative Commons Attribution 4.0 International
License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder in order to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

Funding: EPSRC (EP/G007594/4); Royal Society Industry Fellowship.

Supplementary information accompanies this paper at http://www.nature.com/
scientificreports.

Fingerprint Dive into the research topics of 'Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation'. Together they form a unique fingerprint.

  • Cite this

    Durndell, L., Parlett, C. M. A., Hondow, N. S., Issacs, M. A., Wilson, K., & Lee, A. (2015). Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation. Scientific Reports, 5, 1-9. [9425]. https://doi.org/10.1038/srep09425