Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh

Nirala Singh, Mal Soon Lee, Sneha A. Akhade, Guanhua Cheng, Donald M. Camaioni, Oliver Y. Gutiérrez, Vassiliki Alexandra Glezakou, Roger Rousseau, Johannes A. Lercher, Charles T. Campbell

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

In aqueous phase, the rates of hydrogenation of aromatic substrates such as phenol on Pt/C and Rh/C are influenced by varying activity of hydronium ions. Decreasing the pH from 8 to 1 increases the rate of hydrogenation of phenol on Pt at 20 bar H2 and 80 °C by 15-fold. This increase is attributed to weakening of the hydrogen binding energy (HBE) on the metal surface with decreasing pH. A weaker HBE at lower pH is also predicted by ab initio molecular dynamics simulations, providing atomistic insight into the impact of electrolyte ion distribution and interfacial solvent reorganization on HBE. The lower HBE results in a decrease in the activation energy for addition of adsorbed H from the metal to the adsorbed organic (with a Brønsted-Evans-Polanyi slope of ∼1). The kinetic model derived accounts also for the lack of pH dependence at low hydrogen coverages (at 1 bar H2 on Pt or up to 70 bar H2 on Rh), when the weakening of the HBE decreases the hydrogen coverage.

Original languageEnglish
Pages (from-to)1120-1128
Number of pages9
JournalACS Catalysis
Volume9
Issue number2
DOIs
Publication statusPublished - Feb 1 2019

Fingerprint

Phenol
Phenols
Hydrogenation
Hydrogen
Carbon
Binding energy
Metals
Ions
Electrolytes
Molecular dynamics
Activation energy
Kinetics
Computer simulation
Substrates

Keywords

  • aqueous phase
  • Brønsted-Evans-Polanyi
  • hydrogen adsorption
  • hydrogenation
  • molecular dynamics simulations
  • pH effects
  • phenol
  • platinum

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Singh, N., Lee, M. S., Akhade, S. A., Cheng, G., Camaioni, D. M., Gutiérrez, O. Y., ... Campbell, C. T. (2019). Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. ACS Catalysis, 9(2), 1120-1128. https://doi.org/10.1021/acscatal.8b04039

Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. / Singh, Nirala; Lee, Mal Soon; Akhade, Sneha A.; Cheng, Guanhua; Camaioni, Donald M.; Gutiérrez, Oliver Y.; Glezakou, Vassiliki Alexandra; Rousseau, Roger; Lercher, Johannes A.; Campbell, Charles T.

In: ACS Catalysis, Vol. 9, No. 2, 01.02.2019, p. 1120-1128.

Research output: Contribution to journalArticle

Singh, N, Lee, MS, Akhade, SA, Cheng, G, Camaioni, DM, Gutiérrez, OY, Glezakou, VA, Rousseau, R, Lercher, JA & Campbell, CT 2019, 'Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh', ACS Catalysis, vol. 9, no. 2, pp. 1120-1128. https://doi.org/10.1021/acscatal.8b04039
Singh N, Lee MS, Akhade SA, Cheng G, Camaioni DM, Gutiérrez OY et al. Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. ACS Catalysis. 2019 Feb 1;9(2):1120-1128. https://doi.org/10.1021/acscatal.8b04039
Singh, Nirala ; Lee, Mal Soon ; Akhade, Sneha A. ; Cheng, Guanhua ; Camaioni, Donald M. ; Gutiérrez, Oliver Y. ; Glezakou, Vassiliki Alexandra ; Rousseau, Roger ; Lercher, Johannes A. ; Campbell, Charles T. / Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. In: ACS Catalysis. 2019 ; Vol. 9, No. 2. pp. 1120-1128.
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