A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes

David C. Cantu, Asanga B. Padmaperuma, Manh Thuong Nguyen, Sneha A. Akhade, Yeohoon Yoon, Yang Gang Wang, Mal Soon Lee, Vassiliki Alexandra Glezakou, Roger Rousseau, Michael A. Lilga

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

A detailed mechanistic study of the electrochemical hydrogenation of aldehydes is presented toward the goal of identifying how organic molecules in solution behave at the interface with charged surfaces and what is the best manner to convert them. Specifically, this study focuses on designing an electrocatalytic route for ambient-temperature postpyrolysis treatment of bio-oil. Aldehyde reductions are needed to convert biomass into fuels or chemicals. A combined experimental and computational approach is taken toward catalyst design to provide testable hypotheses regarding catalyst composition, activity, and selectivity. Electrochemical hydrogenation mechanisms for benzaldehyde and pentanal reduction are found to proceed by a coupled proton-electron transfer process. Initial results show that Au, Ag, Cu, and C catalysts exhibit the highest conversion to alcohol products. These catalysts are suitable because they show high cathodic onset potentials for H2 formation and low cathodic onset potentials for organic reduction. Conversion of aromatic aldehydes is found to be appreciably higher than that of aliphatic aldehydes. Classical molecular dynamics simulations of solvent and substrate mixtures in an electrolytic cell were performed to assess how species concentrations vary at the solid/liquid interface and in the bulk as a function of applied voltage. Results show that an increase in surface charge in the electrolytic cell decreases organic and increases water mole fractions at the solid/liquid interface. In this current study, charged cathodic surfaces result in carbonyl orientations at the surface that do not favor electron transfer. Repulsion of organic substrates to the bulk must be compensated by strong adhesion to the electrode surface. Implications on catalyst choice and process design are discussed.

Original languageEnglish
Pages (from-to)7645-7658
Number of pages14
JournalACS Catalysis
Volume8
Issue number8
DOIs
Publication statusPublished - Aug 3 2018

Fingerprint

Aldehydes
Hydrogenation
Catalysts
Electrolytic cells
Electrons
Catalyst selectivity
Liquids
Substrates
Surface charge
Molecular dynamics
Protons
Process design
Catalyst activity
Oils
Biomass
Alcohols
Adhesion
Electrodes
Molecules
Water

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Cantu, D. C., Padmaperuma, A. B., Nguyen, M. T., Akhade, S. A., Yoon, Y., Wang, Y. G., ... Lilga, M. A. (2018). A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes. ACS Catalysis, 8(8), 7645-7658. https://doi.org/10.1021/acscatal.8b00858

A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes. / Cantu, David C.; Padmaperuma, Asanga B.; Nguyen, Manh Thuong; Akhade, Sneha A.; Yoon, Yeohoon; Wang, Yang Gang; Lee, Mal Soon; Glezakou, Vassiliki Alexandra; Rousseau, Roger; Lilga, Michael A.

In: ACS Catalysis, Vol. 8, No. 8, 03.08.2018, p. 7645-7658.

Research output: Contribution to journalArticle

Cantu, DC, Padmaperuma, AB, Nguyen, MT, Akhade, SA, Yoon, Y, Wang, YG, Lee, MS, Glezakou, VA, Rousseau, R & Lilga, MA 2018, 'A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes', ACS Catalysis, vol. 8, no. 8, pp. 7645-7658. https://doi.org/10.1021/acscatal.8b00858
Cantu, David C. ; Padmaperuma, Asanga B. ; Nguyen, Manh Thuong ; Akhade, Sneha A. ; Yoon, Yeohoon ; Wang, Yang Gang ; Lee, Mal Soon ; Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Lilga, Michael A. / A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes. In: ACS Catalysis. 2018 ; Vol. 8, No. 8. pp. 7645-7658.
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