Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

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.

Publication DOI: https://doi.org/10.1038/srep09425
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Energy and Bioproducts Research Institute (EBRI)
College of Engineering & Physical Sciences
Additional Information: 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.
Uncontrolled Keywords: General
Full Text Link:
Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
https://www.nat ... icles/srep09425 (Publisher URL)
PURE Output Type: Article
Published Date: 2015-03-24
Accepted Date: 2015-03-03
Authors: Durndell, Lee
Parlett, Christopher M.A. (ORCID Profile 0000-0002-3651-7314)
Hondow, Nicole S.
Issacs, Mark A.
Wilson, Karen (ORCID Profile 0000-0003-4873-708X)
Lee, Adam (ORCID Profile 0000-0002-2153-1391)

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