On the active sites for the oxygen reduction reaction catalyzed by graphene-based materials

Ljubisa R. Radovic, Adolfo J.A. Salgado-Casanova, Camila V. Mora-Vilches

Research output: Contribution to journalArticle

Abstract

At the heart of the mechanism and efficiency of oxygen reduction is the identification of active sites in graphene-based electrocatalysts ranging from carbon blacks to heat-treated phthalocyanines. Distinction between the transfer of two or four electrons points to O2 dissociation as the essential mechanistic clue; here we examine this issue by exploiting the analogy with carbon oxidation, where production of CO vs. CO2 has long been a crucial point. We compare our computational results with experimental evidence on the behavior of graphene as well as its N-, B- and transition-metal-doped counterparts. Electron transfer is revealed to occur readily through a carbene-type site upon oxygen surface rearrangement. Whether adsorbed O2 dissociates depends on proton transfer occurring before or after the stabilization of a peroxy intermediate; this in turn depends on electron density distribution at and around the active site. A good correlation exists between spin density at the active site and O2 adsorption energy.

Original languageEnglish (US)
Pages (from-to)389-398
Number of pages10
JournalCarbon
Volume156
DOIs
StatePublished - Jan 1 2020

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Graphite
Graphene
Oxygen
Soot
Electronic density of states
Proton transfer
Electrons
Electrocatalysts
Carbon Monoxide
Carbon black
Transition metals
Carbon
Stabilization
Adsorption
Oxidation
Hot Temperature
carbene
phthalocyanine

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)

Cite this

Radovic, Ljubisa R. ; Salgado-Casanova, Adolfo J.A. ; Mora-Vilches, Camila V. / On the active sites for the oxygen reduction reaction catalyzed by graphene-based materials. In: Carbon. 2020 ; Vol. 156. pp. 389-398.
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On the active sites for the oxygen reduction reaction catalyzed by graphene-based materials. / Radovic, Ljubisa R.; Salgado-Casanova, Adolfo J.A.; Mora-Vilches, Camila V.

In: Carbon, Vol. 156, 01.01.2020, p. 389-398.

Research output: Contribution to journalArticle

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AU - Radovic, Ljubisa R.

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