Dramatic increase in the oxygen reduction reaction for platinum cathodes from tuning the solvent dielectric constant

Alessandro Fortunelli, William A. Goddard, Yao Sha, Ted H. Yu, Luca Sementa, Giovanni Barcaro, Oliviero Andreussi

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

Hydrogen fuel cells (FC) are considered essential for a sustainable economy based on carbon-free energy sources, but a major impediment are the costs. First-principles quantum mechanics (density functional theory including solvation) is used to predict how the energies and barriers for the mechanistic steps of the oxygen reduction reaction (ORR) over the fcc(111) platinum surface depend on the dielectric constant of the solvent. The ORR kinetics can be strongly accelerated by decreasing the effective medium polarizability from the high value it has in water. Possible ways to realize this experimentally are suggested. The calculated volcano structure for the dependence of rate on solvent polarization is considered to be general, and should be observed in other electrochemical systems. Hydrogen fuel cell: The oxygen reduction reaction (ORR) kinetics can be strongly accelerated by changing the solvent and its dielectric constant, a possibly general effect in electrochemical systems. The influence of the solvent dielectric constant on the reaction barriers of the ORR is studied by density functional theory (see picture).

Original languageEnglish
Pages (from-to)6669-6672
Number of pages4
JournalAngewandte Chemie - International Edition
Volume53
Issue number26
DOIs
StatePublished - 23 Jun 2014

Keywords

  • density functional calculations
  • electrochemistry
  • hydrogen fuel cells
  • reaction energy barriers
  • solvation

Fingerprint

Dive into the research topics of 'Dramatic increase in the oxygen reduction reaction for platinum cathodes from tuning the solvent dielectric constant'. Together they form a unique fingerprint.

Cite this