Observation of an Inverse Kinetic Isotope Effect in Oxygen Evolution Electrochemistry

Edmund C.M. Tse, Thao T.H. Hoang, Jason A. Varnell, Andrew A. Gewirth

Research output: Contribution to journalArticlepeer-review


Earth-abundant and inexpensive catalysts with low overpotential and high durability are central to the development of efficient water-splitting electrolyzers. However, improvements in catalyst design and preparation are currently hampered by the lack of a detailed understanding of the reaction mechanisms of the oxygen evolution reaction (OER) facilitated by nonprecious-metal (NPM) catalysts. In this paper, we conducted a kinetic isotope effect (KIE) study in an effort to identify the rate-determining step (RDS) of these intricate electrocatalytic reactions involving multiple proton-coupled electron transfer (PCET) processes. We observed an inverse KIE for OER catalyzed by Ni and Co electrodes. These results contribute to a more complete understanding of the OER mechanism and allow for the future development of improved NPM catalysts.

Original languageEnglish (US)
Pages (from-to)5706-5714
Number of pages9
JournalACS Catalysis
Issue number9
StatePublished - Sep 2 2016


  • electrocatalysis
  • kinetic isotope effect
  • nonprecious metal
  • oxygen evolution reaction
  • proton-coupled electron transfer
  • reaction mechanism
  • water oxidation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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