Platinum catalysed aerobic selective oxidation of cinnamaldehyde to cinnamic acid


Aerobic selective oxidation of allylic aldehydes offers an atom and energy efficient route to unsaturated carboxylic acids, however suitable heterogeneous catalysts offering high selectivity and productivity have to date proved elusive. Herein, we demonstrate the direct aerobic oxidation of cinnamaldehyde to cinnamic acid employing silica supported Pt nanoparticles under base-free, batch and continuous flow operation. Surface and bulk characterisation of four families of related Pt/silica catalysts by XRD, XPS, HRTEM, CO chemisorption and N2 porosimetry evidence surface PtO2 as the common active site for cinnamaldehyde oxidation, with a common turnover frequency of 49,000 ± 600 h−1; competing cinnamaldehyde hydrogenolysis is favoured over metallic Pt. High area mesoporous (SBA-15 or KIT-6) and macroporous-mesoporous SBA-15 silicas confer significant rate and cinnamic acid yield enhancements versus low area fumed silica, due to superior platinum dispersion. High oxygen partial pressures and continuous flow operation stabilise PtO2 active sites against in-situ reduction and concomitant deactivation, further enhancing cinnamic acid productivity.

Publication DOI:
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: © 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International Funding: EPSRC (EP/G007594/4, EP/K014749/1 and EP/K014676/1).
Uncontrolled Keywords: Platinum,Cinnamaldehyde,Oxidation,Porous,Silica
Publication ISSN: 1873-4308
Last Modified: 29 Apr 2024 07:23
Date Deposited: 05 Mar 2018 11:25
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Related URLs: http://linkingh ... 920586118301457 (Publisher URL)
PURE Output Type: Article
Published Date: 2019-08-01
Published Online Date: 2018-03-01
Accepted Date: 2018-02-27
Authors: Durndell, Lee J.
Cucuzzella, Costanza
Parlett, Christopher M.a. (ORCID Profile 0000-0002-3651-7314)
Isaacs, Mark A.
Wilson, Karen
Lee, Adam F.

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