An update on the mechanism of the graphene-NO reaction

Andrea M. Oyarzún, Ljubisa R. Radovic, Takashi Kyotani

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Abstract Cognizant of the key experimental facts from studies of carbonaceous solids ranging from soot to graphite, we performed a quantum chemistry study of the interaction of NO monomer or dimer with one or more zigzag sites. Thermodynamic and kinetic results were used to examine two alternative mechanisms proposed in the literature, and to compare them with the graphene-O2 reaction mechanism. The chemisorption stoichiometry similarities are striking; but the differences, especially regarding the intermediate role of N2O, have important practical implications. Monomer chemisorption on an isolated site is a dead-end and temporarily inhibiting process, similar to that of formation of a stable C-O surface complex in the graphene-O2 reaction. When two sites are available, successive monomer adsorption eventually leads to N2O formation subsequent to parallel reorientation of the first NO molecule. If three contiguous sites are available, N2 and CO are the principal products. Chemisorption of the dimer provides a straightforward path to N2 and CO2 when one site is available and to N2 and CO when two sites are available. The formation of N2O is also feasible in this case, both during adsorption and desorption; in the adsorption phase it is very sensitive to the details of the electron pairing processes.

Original languageEnglish (US)
Article number9644
Pages (from-to)58-68
Number of pages11
JournalCarbon
Volume86
DOIs
StatePublished - May 1 2015

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Graphite
Chemisorption
Graphene
Monomers
Carbon Monoxide
Adsorption
Dimers
Soot
Quantum chemistry
Stoichiometry
Desorption
Thermodynamics
Molecules
Kinetics
Electrons

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Oyarzún, Andrea M. ; Radovic, Ljubisa R. ; Kyotani, Takashi. / An update on the mechanism of the graphene-NO reaction. In: Carbon. 2015 ; Vol. 86. pp. 58-68.
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An update on the mechanism of the graphene-NO reaction. / Oyarzún, Andrea M.; Radovic, Ljubisa R.; Kyotani, Takashi.

In: Carbon, Vol. 86, 9644, 01.05.2015, p. 58-68.

Research output: Contribution to journalArticle

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