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Structure and chemical reactivity of lithium-doped graphene on hydrogen-saturated silicon carbide

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Abstract

Herein, we studied the structure and hydrogenation of graphene supported on hydrogen-terminated SiC, with intercalated Li atoms. Strong nonbonded interactions occur between graphene and the Si–H groups. The latter were found to be significantly augmented by the intercalation of Li atoms, which enhanced the SiH::pi interactions. Although the electronic structure of graphene did not experience significant changes when supported on hydrogen-terminated SiC, a small gap of 0.04 eV was computed at the HSEH1PBE/6-31G* level. The clustering of Li atoms over graphene was prevented by the SiC support. A significant enhancement of reactivity could be corroborated due to the presence of intercalated Li atoms, given that the C–H binding energy was increased by almost 1 eV with respect to pristine graphene. We expect that hydrogen-terminated SiC with intercalated Li atoms can be used to enhance the chemical reactivity of graphene, given that it strongly interacts with graphene but does not compete for the electrons donated by Li.

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References

  1. Denis PA, Iribarne F (2011) Comparative study of defect reactivity in graphene. J Phys Chem C 117:19048–19055

    Article  Google Scholar 

  2. Denis PA (2013) Organic chemistry of graphene: the Diels–Alder reaction. Chem Eur J 19:15719–15725

    Article  Google Scholar 

  3. Cao Y, Osuna S, Liang Y, Haddon RC, Houk KN (2013) Diels-Alder reactions of graphene: computational predictions of products and sites of reaction. J Am Chem Soc 135:17643–17649

    Article  Google Scholar 

  4. Fan X, Nouchi R, Tanigaki K (2011) Effect of charge puddles and ripples on the chemical reactivity of single layer graphene supported by SiO2/Si substrate. J Phys Chem C 115:12960–12964

    Article  Google Scholar 

  5. Gao X, Wang Y, Liu X, Chan TL, Irle S, Zhao Y, Zhang SB (2011) Regioselectivity control of graphene functionalization by ripples. Phys Chem Chem Phys 13:19449–19453

    Article  Google Scholar 

  6. Denis PA, Pereyra C (2015) Structural characterization and chemical reactivity of dual doped graphene. Carbon 87:106–115

    Article  Google Scholar 

  7. Denis PA, Pereyra C, Iribarne F (2014) Theoretical characterization of sulfur and nitrogen dual-doped graphene. Comp Theor Chem 1049:13–19

    Article  Google Scholar 

  8. Denis PA (2014) Chemical reactivity and band-gap opening of graphene doped with gallium, germanium, arsenic, and selenium atoms. ChemPhysChem 15:3994–4000

    Article  Google Scholar 

  9. Ferrighi L, Datteo M, Di Valentin C (2014) Boosting graphene reactivity with oxygen by boron doping: density functional theory modeling of the reaction path. J Phys Chem C 118:223–230

    Article  Google Scholar 

  10. Chua CK, Sofer Z, Luxa J, Pumera M (2015) Selective nitrogen functionalization of graphene by Bucherer-type reaction. Chem Eur J 21:8090–8095

    Article  Google Scholar 

  11. Denis PA (2011) Chemical reactivity of lithium doped monolayer and bilayer graphene. J Phys Chem C 115:13392–13398

    Article  Google Scholar 

  12. Tapia A, Acosta C, Medina-Esquivel RA, Canto G (2011) Potassium influence in the adsorption of hydrogen on graphene: a density functional theory study. Comput Mater Sci 50:2427–2432

    Article  Google Scholar 

  13. Logsdail AJ, Johnston RL, Akola J (2013) Improving the adsorption of Au Atoms and nanoparticles on graphite via Li intercalation. J Phys Chem C 117:22683–22695

    Article  Google Scholar 

  14. Huang LF, Ni MY, Zhang GR, Zhou WH, Li YG, Zheng XH, Zeng Z (2011) Modulation of the thermodynamic, kinetic, and magnetic properties of the hydrogen monomer on graphene by charge doping. J Chem Phys 135:064705

    Article  Google Scholar 

  15. Huang LF, Cao TF, Gong PL, Zeng A, Zhang C (2012) Tuning the adatom-surface and interadatom interactions in hydrogenated graphene by charge doping. Phys Rev B 86:125433

    Article  Google Scholar 

  16. Denis PA (2013) Chemical reactivity of electron-doped and hole-doped graphene. J Phys Chem C 11:3895–3902

    Article  Google Scholar 

  17. Denis PA, Iribarne F (2015) Strong N-doped graphene: the case of 4-(1, 3-Dimethyl-2, 3-dihydro-1 H-benzoimidazol-2-yl) phenyl) dimethylamine (N-DMBI). J Phys Chem C 119:5770–5777

    Article  Google Scholar 

  18. Ambrosetti A, Silvestry PL (2016) Enhanced chemical reactivity of graphene on a Ni(111) substrate. J Chem Phys 144:111101

    Article  Google Scholar 

  19. Zhao W, Gebhardt J, Spath F, Gotterbarm K, Gleichweit C, Steiruck HP, Gorling A, Papp C (2015) Reversible hydrogenation of graphene on Ni(111)—synthesis of “graphone”. Chem Eur J 21:3347

    Article  Google Scholar 

  20. Wang QH, Jin Z, Kim K, Hilmer AJ, Paulus GLC, Shih CJ, Ham MH, Sanchez-Yamagishi JD, Watanabe K, Taniguchi T, Kong J, Jarillo-Hererro P, Strano MS (2012) Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography. Nat Chem 4:724–732

    Article  Google Scholar 

  21. Ding Y, Peng Q, Gan L, Wu R, Ou X, Zhang Q, Luo Z (2016) Stacking modes induced reactivity enhancement for twisted bilayer graphene. Chem Mat 28:1034

    Article  Google Scholar 

  22. Dion M, Rydberg H, Schroder E, Langreth DC, Lundqvist BI (2004) Van der Waals density functional for general geometries. Phys Rev Lett 92:246401

    Article  Google Scholar 

  23. Soler JM, Artacho E, Gale JD, Garcia A, Junquera J, Ordejon P, Sanchez-Portal D (2002) The SIESTA method for Ab initio order-N materials simulation. J Phys 14:2745–2779

    Google Scholar 

  24. Ordejon P, Artacho E, Soler JM (1996) Self-consistent order-N density-functional Calculations for very large systems. Phys Rev B 53:R10441–R10444

    Article  Google Scholar 

  25. Boys FS, Bernardi F (1970) The calculation of small molecular interactions by the differences of separate total energies. Mol Phys 19:553–566

    Article  Google Scholar 

  26. Denis PA (2009) Denisty functional investigation of thiolated and thioepoxidated graphene. J Phys Chem C 113:5612–5619

    Article  Google Scholar 

  27. Troullier N, Martins JL (1991) efficient pseudopotentials for plane-wave calculations. Phys Rev B 43:1993–2006

    Article  Google Scholar 

  28. Denis PA, Iribarne F (2012) Cooperative behavior in functionalized graphene: explaining the occurrence of 1,3 cycloaddition of azomethine ylides onto graphene. Chem Phys Lett 550:111–117

    Article  Google Scholar 

  29. Zhao Y, Truhlar DG (2006) A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J Chem Phys 125:194101

    Article  Google Scholar 

  30. Zhao Y, Truhlar DG (2008) Density functionals with broad applicability in chemistry. Theor Chem Account 120:215–241

    Article  Google Scholar 

  31. Heyd J, Scuseria GE (2004) Assessment and validation of a screened coulomb hybrid density functional. J Chem Phys 120:7274–7280

    Article  Google Scholar 

  32. Barone V, Scuseria GE (2004) Theoretical Study of the electronic properties of narrow single-walled carbon nanotubes: beyond the local density approximation. J Chem Phys 121:10376–10379

    Article  Google Scholar 

  33. Hehre W, Radom L, PvR Schleyer, Pople JA (1986) Ab initio molecular orbital theory. Wiley, New Work

    Google Scholar 

  34. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2009) Gaussian 09, revision D. Gaussian, Inc, Wallingford

    Google Scholar 

  35. Sun GF, Xia JF, Xue QK, Li L (2009) Nanotechnology 20:335701

    Article  Google Scholar 

  36. Halle J, Neel N, Kroger J (2016) Filling the gap: Li-intercalated graphene on Ir(111). J Phys Chem C 120:5067

    Article  Google Scholar 

  37. Vezin B, Dugourd P, Rayane D, Labastie P, Broyer M (1993) First observation of an excited state of Li2H. Chem Phys Lett 202:209–215

    Article  Google Scholar 

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Acknowledgements

The author thanks PEDECIBA Quimica, CSIC, and ANII for financial support.

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Authors and Affiliations

  1. Computational Nanotechnology, DETEMA, Facultad de Química, UDELAR, CC 1157, 11800, Montevideo, Uruguay

    Pablo A. Denis

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  1. Pablo A. Denis
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Correspondence to Pablo A. Denis.

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Denis, P.A. Structure and chemical reactivity of lithium-doped graphene on hydrogen-saturated silicon carbide. J Mater Sci 52, 1348–1356 (2017). https://doi.org/10.1007/s10853-016-0429-z

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  • DOI: https://doi.org/10.1007/s10853-016-0429-z

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