Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/102241
Title: Charge transfer and weak bonding between molecular oxygen and graphene zigzag edges at low temperatures
Authors: Boukhvalov, D. W.
Osipov, V. Y.
Shames, A. I.
Takai, K.
Hayashi, T.
Enoki, T.
Issue Date: 2016
Publisher: Elsevier Ltd
Citation: Charge transfer and weak bonding between molecular oxygen and graphene zigzag edges at low temperatures / D. W. Boukhvalov, V. Y. Osipov, A. I. Shames, et al. — DOI 10.1016/j.carbon.2016.06.020 // Carbon. — 2016. — Vol. 107. — P. 800-810.
Abstract: Electron paramagnetic resonance (EPR) study of air-physisorbed defective carbon nano-onions evidences in favor of microwave assisted formation of weakly-bound paramagnetic complexes comprising negatively-charged O2− ions and edge carbon atoms carrying π-electronic spins. These complexes being located on the graphene edges are stable at low temperatures but irreversibly dissociate at temperatures above 50–60 K. These EPR findings are justified by density functional theory (DFT) calculations demonstrating transfer of an electron from the zigzag edge of graphene-like material to oxygen molecule physisorbed on the graphene sheet edge. This charge transfer causes changing the spin state of the adsorbed oxygen molecule from S = 1 to S = 1/2 one. DFT calculations show significant changes of adsorption energy of oxygen molecule and robustness of the charge transfer to variations of the graphene-like substrate morphology (flat and corrugated mono- and bi-layered graphene) as well as edges’ passivation. The presence of H- and COOH- terminated edge carbon sites with such a corrugated substrate morphology allows formation of ZE–O2− paramagnetic complexes characterized by small (<50 meV) binding energies and also explains their irreversible dissociation as revealed by EPR. © 2016
Keywords: BINDING ENERGY
BINDING SITES
CHARGE TRANSFER
CHEMICAL BONDS
DENSITY FUNCTIONAL THEORY
ELECTRON SPIN RESONANCE SPECTROSCOPY
LIGHT POLARIZATION
MAGNETIC RESONANCE
MOLECULAR OXYGEN
MOLECULES
OXYGEN
PARAMAGNETIC RESONANCE
PARAMAGNETISM
SUBSTRATES
ADSORPTION ENERGIES
CORRUGATED SUBSTRATES
ELECTRON PARAMAGNETIC RESONANCES (EPR)
IRREVERSIBLE DISSOCIATION
MICROWAVE ASSISTED
NEGATIVELY CHARGED
PARAMAGNETIC COMPLEXES
SUBSTRATE MORPHOLOGIES
GRAPHENE
URI: http://hdl.handle.net/10995/102241
Access: info:eu-repo/semantics/openAccess
SCOPUS ID: 84976580770
PURE ID: 1025337
306bb60a-50e9-434b-9807-a1eee1fa46fe
ISSN: 86223
DOI: 10.1016/j.carbon.2016.06.020
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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