Understanding the role of metal and molecular structure on the electrocatalytic hydrogenation of oxygenated organic compounds

Juan A. Lopez-Ruiz, Evan Andrews, Sneha A. Akhade, Mal Soon Lee, Katherine Koh, Udishnu Sanyal, Simuck F. Yuk, Abhijeet J. Karkamkar, Miroslaw A. Derewinski, Johnathan Holladay, Vassiliki Alexandra Glezakou, Roger Rousseau, Oliver Y. Gutiérrez, Jamie D. Holladay

Research output: Contribution to journalArticle

Abstract

Electrocatalytic hydrogenation is increasingly studied as an alternative to integrate the use of recycled carbon feedstocks with renewable energy sources. However, the abundant empiric observations available have not been correlated with fundamental properties of substrates and catalysts. In this study, we investigated electrocatalytic hydrogenation of a homologues series of carboxylic acids, ketones, phenolics, and aldehydes on a variety of metals (Pd, Rh, Ru, Cu, Ni, Zn, and Co). We found that the rates of carbonyl reduction in aldehydes correlate with the corresponding binding energies between the aldehydes and the metals according to the Sabatier principle. That is, the highest rates are obtained at intermediate binding energies. The rates of H2 evolution that occurs in parallel to hydrogenation also correlate with the H-metal binding energies, following the same volcano-type behavior. Within the boundaries of this model (e.g., compounds reactive at room temperature and without important steric effects over the carbonyl group), the reported correlations help to explain the complex trends derived from the experimental observations, allowing for the correlation of rates with binding energies and the differentiation of mechanistic routes.

Original languageEnglish
JournalACS Catalysis
DOIs
Publication statusAccepted/In press - Jan 1 2019

Fingerprint

Binding energy
Organic compounds
Molecular structure
Hydrogenation
Metals
Aldehydes
Volcanoes
Carboxylic Acids
Ketones
Carboxylic acids
Feedstocks
Carbon
Catalysts
Substrates
Temperature

Keywords

  • Electrocatalytic hydrogenation
  • H2 evolution
  • Sabatier principle
  • Theoretical thermodynamic descriptors

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Lopez-Ruiz, J. A., Andrews, E., Akhade, S. A., Lee, M. S., Koh, K., Sanyal, U., ... Holladay, J. D. (Accepted/In press). Understanding the role of metal and molecular structure on the electrocatalytic hydrogenation of oxygenated organic compounds. ACS Catalysis. https://doi.org/10.1021/acscatal.9b02921

Understanding the role of metal and molecular structure on the electrocatalytic hydrogenation of oxygenated organic compounds. / Lopez-Ruiz, Juan A.; Andrews, Evan; Akhade, Sneha A.; Lee, Mal Soon; Koh, Katherine; Sanyal, Udishnu; Yuk, Simuck F.; Karkamkar, Abhijeet J.; Derewinski, Miroslaw A.; Holladay, Johnathan; Glezakou, Vassiliki Alexandra; Rousseau, Roger; Gutiérrez, Oliver Y.; Holladay, Jamie D.

In: ACS Catalysis, 01.01.2019.

Research output: Contribution to journalArticle

Lopez-Ruiz, JA, Andrews, E, Akhade, SA, Lee, MS, Koh, K, Sanyal, U, Yuk, SF, Karkamkar, AJ, Derewinski, MA, Holladay, J, Glezakou, VA, Rousseau, R, Gutiérrez, OY & Holladay, JD 2019, 'Understanding the role of metal and molecular structure on the electrocatalytic hydrogenation of oxygenated organic compounds', ACS Catalysis. https://doi.org/10.1021/acscatal.9b02921
Lopez-Ruiz, Juan A. ; Andrews, Evan ; Akhade, Sneha A. ; Lee, Mal Soon ; Koh, Katherine ; Sanyal, Udishnu ; Yuk, Simuck F. ; Karkamkar, Abhijeet J. ; Derewinski, Miroslaw A. ; Holladay, Johnathan ; Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Gutiérrez, Oliver Y. ; Holladay, Jamie D. / Understanding the role of metal and molecular structure on the electrocatalytic hydrogenation of oxygenated organic compounds. In: ACS Catalysis. 2019.
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