Platinum catalysed aerobic selective oxidation of cinnamaldehyde to cinnamic acid

Durndell, Lee J., Cucuzzella, Costanza, Parlett, Christopher M.a., Isaacs, Mark A., Wilson, Karen and Lee, Adam F. (2018). Platinum catalysed aerobic selective oxidation of cinnamaldehyde to cinnamic acid. Catalysis Today ,

Abstract

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: https://doi.org/10.1016/j.cattod.2018.02.052
Divisions: Engineering & Applied Sciences
Engineering & Applied Sciences > Chemical engineering & applied chemistry
Engineering & Applied Sciences > European Bioenergy Research Institute (EBRI)
Additional Information: © 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/. Funding: EPSRC (EP/G007594/4, EP/K014749/1 and EP/K014676/1).
Uncontrolled Keywords: Platinum; Cinnamaldehyde; Oxidation; Porous; Silica
Full Text Link: http://linkingh ... 920586118301457
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Published Date: 2018-03-01
Published Online Date: 2018-03-01
Authors: Durndell, Lee J.
Cucuzzella, Costanza
Parlett, Christopher M.a. ( 0000-0002-3651-7314)
Isaacs, Mark A.
Wilson, Karen ( 0000-0003-4873-708X)
Lee, Adam F. ( 0000-0002-2153-1391)

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