Identification of slow relaxing spin components by pulse EPR techniques in graphene-related materials

Antonio Barbon; Francesco Tampieri; Antonio Barbon; Francesco Tampieri

doi:10.3934/matersci.2017.1.147

AIMS Materials Science

2017, Volume 4, Issue 1: 147-157. doi: 10.3934/matersci.2017.1.147

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Identification of slow relaxing spin components by pulse EPR techniques in graphene-related materials

Antonio Barbon ^,,
Francesco Tampieri

Department of Chemical Science, University of Padova, Via Marzolo 1, 35131 Padova, Italy

Received: 07 November 2016 Accepted: 10 January 2017 Published: 13 January 2017

Electron Paramagnetic Resonance (EPR) is a powerful technique that is suitable to study graphene-related materials. The challenging ability requested to the spectroscopy is its capability to resolve the variety of structures, relatively similar, that are obtained in materials produced through different methods, but that also coexist inside a single sample. In general, because of the intrinsic inhomogeneity of the samples, the EPR spectra are therefore a superposition of spectra coming from different structures. We show that by pulse EPR techniques (echo-detected EPR, ESEEM and Mims ENDOR) we can identify and characterize species with slow spin relaxing properties. These species are generally called molecular states, and are likely small pieces of graphenic structures of limited dimensions, thus conveniently described by a molecular approach. We have studied commercial reduced graphene oxide and chemically exfoliated graphite, which are characterized by different EPR spectra. Hyperfine spectroscopies enabled us to characterize the molecular components of the different materials, especially in terms of the interaction of the unpaired electrons with protons (number of protons and hyperfine coupling constants). We also obtained useful precious information about extent of delocalization of the molecular states.
- graphenic-related materials,
- RGO,
- exfoliated graphite,
- pulse EPR
Citation: Antonio Barbon, Francesco Tampieri. Identification of slow relaxing spin components by pulse EPR techniques in graphene-related materials[J]. AIMS Materials Science, 2017, 4(1): 147-157. doi: 10.3934/matersci.2017.1.147

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Abstract

Electron Paramagnetic Resonance (EPR) is a powerful technique that is suitable to study graphene-related materials. The challenging ability requested to the spectroscopy is its capability to resolve the variety of structures, relatively similar, that are obtained in materials produced through different methods, but that also coexist inside a single sample. In general, because of the intrinsic inhomogeneity of the samples, the EPR spectra are therefore a superposition of spectra coming from different structures. We show that by pulse EPR techniques (echo-detected EPR, ESEEM and Mims ENDOR) we can identify and characterize species with slow spin relaxing properties. These species are generally called molecular states, and are likely small pieces of graphenic structures of limited dimensions, thus conveniently described by a molecular approach. We have studied commercial reduced graphene oxide and chemically exfoliated graphite, which are characterized by different EPR spectra. Hyperfine spectroscopies enabled us to characterize the molecular components of the different materials, especially in terms of the interaction of the unpaired electrons with protons (number of protons and hyperfine coupling constants). We also obtained useful precious information about extent of delocalization of the molecular states.

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