Research article Topical Sections

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

  • 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.

    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

    Related Papers:

  • 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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    [1] Quesnel E, Roux F, Emieux F, et al. (2015) Graphene-based technologies for energy applications, challenges and perspectives. 2D Mater 2: 030204. doi: 10.1088/2053-1583/2/3/030204
    [2] Chen A, Hutchby J, Zhirnov V, et al. (2014) Emerging nanoelectronic devices, John Wiley & Sons.
    [3] Mattei TA, Rehman AA (2014) Technological developments and future perspectives on graphene-based metamaterials: a primer for neurosurgeons. Neurosurgery 74: 499–516. doi: 10.1227/NEU.0000000000000302
    [4] Ray S (2015) Applications of graphene and graphene-oxide based nanomaterials, William Andrew.
    [5] Higgins D, Zamani P, Yu A, et al. (2016) The application of graphene and its composites in oxygen reduction electrocatalysis: a perspective and review of recent progress. Energ Environ Sci 9: 357–390. doi: 10.1039/C5EE02474A
    [6] Ferrari AC, Bonaccorso F, Fal'Ko V, et al. (2015) Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Nanoscale 7: 4598–4810. doi: 10.1039/C4NR01600A
    [7] Novoselov KS, Geim AK, Morozov SV, et al. (2004) Electric field effect in atomically thin carbon films. Science 306: 666–669. doi: 10.1126/science.1102896
    [8] Hummers Jr WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80: 1339–1339. doi: 10.1021/ja01539a017
    [9] Tampieri F, Silvestrini S, Riccò R, et al. (2014) A comparative electron paramagnetic resonance study of expanded graphites and graphene. J Mater Chem C 2: 8105–8112. doi: 10.1039/C4TC01383B
    [10] Ching W, Rulis P (2012) Electronic Structure Methods for Complex Materials: The orthogonalized linear combination of atomic orbitals, Oxford University Press.
    [11] Yoon K, Rahnamoun A, Swett JL, et al. (2016) Atomistic-Scale Simulations of Defect Formation in Graphene under Noble Gas Ion Irradiation. ACS Nano 10: 8376–8384. doi: 10.1021/acsnano.6b03036
    [12] Ferrari A, Meyer J, Scardaci V, et al. (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97: 187401. doi: 10.1103/PhysRevLett.97.187401
    [13] Badenhorst H (2014) Microstructure of natural graphite flakes revealed by oxidation: limitations of XRD and Raman techniques for crystallinity estimates. Carbon 66: 674–690. doi: 10.1016/j.carbon.2013.09.065
    [14] Pardini L, Löffler S, Biddau G, et al. (2016) Mapping atomic orbitals with the transmission electron microscope: Images of defective graphene predicted from first-principles theory. Phys Rev Lett 117: 036801. doi: 10.1103/PhysRevLett.117.036801
    [15] Ćirić L, Sienkiewicz A, Nafradi B, et al. (2009) Towards electron spin resonance of mechanically exfoliated graphene. Phys Status Solidi B 246: 2558–2561. doi: 10.1002/pssb.200982325
    [16] McClure J (1957) Band structure of graphite and de Haas-van Alphen effect. Phys Rev 108: 612. doi: 10.1103/PhysRev.108.612
    [17] Wagoner G (1960) Spin resonance of charge carriers in graphite. Phys Rev 118: 647. doi: 10.1103/PhysRev.118.647
    [18] Nair R, Sepioni M, Tsai I, et al. (2012) Spin-half paramagnetism in graphene induced by point defects. Nat Phys 8: 199–202. doi: 10.1038/nphys2183
    [19] Tommasini M, Castiglioni C, Zerbi G, et al. (2011) A joint Raman and EPR spectroscopic study on ball-milled nanographites. Chem Phys Lett 516: 220–224. doi: 10.1016/j.cplett.2011.09.094
    [20] Barbon A, Brustolon M (2012) An EPR Study on Nanographites. Appl Magn Reson 42: 197–210. doi: 10.1007/s00723-011-0285-6
    [21] Makarova T, Palacio F (2006) Carbon based magnetism: an overview of the magnetism of metal free carbon-based compounds and materials, Elsevier Science.
    [22] Osipov VY, Shames A, Enoki T, et al. (2009) Magnetic and EPR studies of edge-localized spin paramagnetism in multi-shell nanographites derived from nanodiamonds. Diam Relat Mater 18: 220–223. doi: 10.1016/j.diamond.2008.09.015
    [23] Augustyniak-Jabłokow MA, Tadyszak K, Maćkowiak M, et al. (2012) ESR study of spin relaxation in graphene. Chem Phys Lett 557: 118–122.
    [24] Tadyszak K, Augustyniak-Jabłokow MA, Więckowski AB, et al. (2015) Origin of electron paramagnetic resonance signal in anthracite. Carbon 94: 53–59. doi: 10.1016/j.carbon.2015.06.057
    [25] Makarova T, Shelankov A, Zyrianova A, et al. (2015) Edge state magnetism in zigzag-interfaced graphene via spin susceptibility measurements. Sci Rep 5: 13382. doi: 10.1038/srep13382
    [26] Collauto A, Mannini M, Sorace L, et al. (2012) A slow relaxing species for molecular spin devices: EPR characterization of static and dynamic magnetic properties of a nitronyl nitroxide radical. J Mater Chem 22: 22272–22281. doi: 10.1039/c2jm35076a
    [27] Marrale M, Longo A, Brai M, et al. (2011) Pulsed EPR analysis of tooth enamel samples exposed to UV and γ-radiations. Radiat Measur 46: 789–792. doi: 10.1016/j.radmeas.2011.05.020
    [28] Brustolon M, Barbon A (2003) Pulsed EPR of Paramagnetic Centers in Solid Phases, In: Lund A EPR of Free Radicals in Solids, Springer, 39–93.
    [29] Barbon A, Brustolon M, Maniero A, et al. (1999) Dynamics and spin relaxation of tempone in a host crystal. An ENDOR, high field EPR and electron spin echo study. Phys Chem Chem Phys 1: 4015–4023.
    [30] Mims W (1965) Pulsed ENDOR experiments. Proc R Soc Lond A 283: 452–457. doi: 10.1098/rspa.1965.0034
    [31] Schweiger A, Jeschke G (2001) Principles of pulse electron paramagnetic resonance, Oxford University Press.
    [32] Weil JA, Bolton JR (2007) Electron paramagnetic resonance: elementary theory and practical applications, John Wiley & Sons.
    [33] Lewis IC, Singer L (1965) Electron spin resonance of radical cations produced by the oxidation of aromatic hydrocarbons with SbCl5. J Chem Phys 43: 2712–2727. doi: 10.1063/1.1697200
    [34] Janata J, Gendell J, Ling C, et al. (1967) Concerning the anion and cation radicals of corannulene. J Am Chem Soc 89: 3056–3058. doi: 10.1021/ja00988a050
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