Abstract
Density functional theory (DFT) calculations are performed to analyze curvature effects in the oxidative longitudinal unzipping of carbon nanotubes (CNTs) of different diameters. The reactions considered involve the adsorption of permanganate, followed by the oxidation of the nanotube, which results in dione and hole formation. The study was performed with armchair CNTs of different diameters and with corrugated graphene layers, which emulate the curvature of CNT of larger radii, with the finding that the curvature and the pyramidalization angle of the these structures strongly affects the stability of the intermediate dione structure formed during the unzipping process. Permanganate adsorption energies increase for more curved surfaces promoting the oxidation reaction in surfaces of small radius, making this reaction spontaneous for small radius. The second permanganate adsorbs on the parallel carbon–carbon bond to first diona formation resulting the longitudinal unzipping of the CNT.
Similar content being viewed by others
References
Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV (2004) Electric field effect in atomically thin carbon films. Science 306:666–669
Luque GL, Rojas MI, Rivas GA, Leiva EPM (2010) The origin of the catalysis of hydrogen peroxide reduction by functionalized graphene surfaces: a density functional theory study. Electro Acta 56:523–530
Kuila T, Bose S, Khanra P, Mishra AK, Kim NH, Lee JH (2011) Recent advances in graphene-based biosensors. Biosens Bioelec 26(12):4637–4648
Gan T, Hu S (2011) Electrochemical sensors based on graphene materials. Microchim Acta 175:1–19
Hou J, Shao Y, Ellis MW, Moore RB, Yi B (2011) Graphene-based electrochemical energy conversion and storage: fuel cells, supercapacitors and lithium ion batteries. Phys Chem Chem Phys 13(34):15384–15402
Rojas MI, Leiva EPM (2007) Density functional theory study of a graphene sheet modified with titanium in contact with different adsorbates. Phys Rev B 76(15):155415–15523
Sigal A, Rojas MI, Leiva EPM (2011) Interferents for hydrogen storage on graphene sheet decorated with nickel: a DFT study. Inter J Hydrog Energy 36(5):3537–3546
Sigal A, Rojas MI, Leiva EPM (2011) Is hydrogen storage possible in metal-doped graphite 2D systems in conditions found on earth? Phys Rev Lett 107(15):158701–158705
Huang X, Yin Z, Wu S, Qi X, He Q, Zhang Q, Yan Q, Boey F, Zhang H (2011) Graphene-based materials: synthesis, characterization, properties, and applications. Small 7(14):1876–1902
Flynn GW (2011) Perspective: the dawning of the age of graphene. J Chem Phys 135(5):050901–050909
Brownson DAC, Kampouris DK, Banks CE (2012) Graphene electrochemistry: fundamental concepts through to prominent applications. Chem Soc Rev 41:6944–6976
Sridhar V, Jeon J, Oh I (2011) Microwave extraction of graphene from carbon fibers. Carbon 49(1):222–226
Grayfer ED, Makotchenko VG, Nazarov AS, Kim SJ, Fedorov VE (2011) Graphene: chemical approaches to the synthesis and modification. Russ Chem Rev 80(8):751–770
Cho S, Kikuchi K, Kawasaki A (2011) Radial followed by longitudinal unzipping of multiwalled carbon nanotubes. Carbon 49(12):3865–3872
Cataldo F, Compagnini G, Patané C, Ursini O, Angelini G, Ribic PR, Cricenti A, Palleschi G, Valentini F (2010) Graphene nanoribbons produced by the oxidative unzipping of single-wall carbon nanotubes. Carbon 48(9):2596–2602
Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grigorieva IV, Dubonos SV, Firsov AA (2005) Two-dimensional gas of massless Dirac fermions in graphene. Nature 438:197–200
Castro Neto AH, Guinea F, Peres NM, Novoselov KS, Geim AK (2009) The electronic properties of graphene. Rev Modern Phys 81(1):109–162
Acik M, Chabal YJ (2011) Nature of graphene edges: a review. Jap J App Phys 50:070101–070117
Kosynkin DV, Higginbotham AL, Sinitskii A, Lomeda JR, Dimiev A, Price BK, Tour JM (2009) Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature 458:872–876
Higginbotham AL, Kosynkin DV, Sinitskii A, Sun Z, Tour JM (2010) Graphene oxide nanoribbons from multiwalled carbon nanotubes. ACS Nano 4(4):2059–2069
Ramesha GK, Sampath S (2007) Exfoliated graphite oxide modified electrode for the selective determination of picomolar concentration of lead. Electroanalytical 19(23):2472–2478
Bhardwaj T, Antic A, Pavan B, Barone V, Fahlman BD (2010) Enhanced electrochemical lithium storage by graphene nanoribbons. J Am Chem Soc 132:12556–12558
Zhang H, Zhao M, He T, Zhang X, Wang Z, Xi Z, Yan S, Xia Y, Mei L (2010) Orientation-selective unzipping of carbon nanotubes. Phys Chem Chem Phys 12(41):13674–13680
Rangel NL, Sotelo JC, Seminario JM (2009) Mechanism of carbon nanotubes unzipping into graphene ribbons. J Chem Phys 131(3):31105–31109
Titantah JT, Jorissen K, Lamoen D (2004) Density functional theory calculations of energy-loss carbon near-edge spectra of small diameter armchair and zigzag nanotubes: core–hole, curvature, and momentum-transfer orientation effects. Phys Rev B 69:125406–125411
Ordejón P, Artacho E, Soler JM (1996) Self-consistent order-N density-functional calculations for very large systems. Phys Rev B 53(16):R10441–R10444
Soler JM, Artacho E, Gale JD, García A, Junquera J, Ordejón P, Sánchez-Portal D (2002) The SIESTA method for ab initio order-N materials simulation. J Phys Condens Matter 14(11):2745–2779
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77(18):3865–3868
Troullier N, Martins JL (1991) Efficient pseudopotentials for plane-wave calculations. Phys Rev B 43(3):1993–2006
Kleinman L, Bylander DM (1982) Efficacious form for model pseudopotentials. Phys Rev Lett 48(20):1425–1428
Press WH, Flannery BP, Teukolsky SA, Vetterling WT (1986) Numerical recipes: the art of scientific computing. Cambridge University Press, Cambridge
Szabo A, Ostlund NS (1989) Modern quantum chemistry. Graw-Hill, New York
Robertson DH, Brenner DW, Mintmire JW (1992) Energetics of nanoscale graphitic tubules. Phys Rev B 45(21):12592–12595
Tibbets GG (1984) Why are carbon filaments tubular? J Cryst Growth 66(3):632–638
Gülseren O, Yildirim T, Ciraci S (2002) Systematic ab initio study of curvature effects in carbon nanotubes. Phys Rev B 65(15):153405–153409
Sánchez-Portal D, Artacho E, Soler J, Rubio A, Ordejón P (1999) Ab initio structural, elastic, and vibrational properties of carbon nanotubes. Phys Rev B 59(19):12678–12688
Haddon RC (1993) Chemistry of the fullerenes: the manifestation of strain in a class of continuous aromatic molecules. Science 261:1545–1550
Niyogi S, Hamon MA, Hu H, Zhao B, Bhowmik P, Sen R, Itkis ME, Haddon RC (2002) Chemistry of single-walled carbon nanotubes. Acc Chem Res 35:1105–1113
Dinadayalane TC, Leszczynski J (2007) Towars nanomaterials: structural, energetic and reactivity aspects of single-walled carbon nanotubes. In: Balbuena P, Seminario JM (eds) Nanomaterials: design and simulation, 1st edn. Elsevier, Italy, pp 167–201
Haddon RC (1986) Hybridization and the orientation and alignment of.pi.-orbitals in nonplanar conjugated organic molecules:pi.-orbital axis vector analysis (POAV2). J Am Chem Soc 108(11):2837–2842
Haddon RC (2001) Comment on the relationship of the pyramidalization angle at a conjugated carbon atom to the σ bond angles. J Phys Chem B 105:4164–4165
Sun CH, Finnerty JJ, Lu GQ, Cheng HM (2005) Stability of supershort single-walled carbon nanotubes. J Phys Chem B 109:12406–12409
Acknowledgments
This work was supported by PIP 11420090100066 CONICET, PICT 2010-1824, PME 2006-1581, SECyT UNC, Argentina.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Luque, G.L., Rojas, M.I. & Leiva, E.P.M. Curvature effect in the longitudinal unzipping carbon nanotubes. J Solid State Electrochem 17, 1189–1200 (2013). https://doi.org/10.1007/s10008-012-1992-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10008-012-1992-0