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N–H bond cleavage of ammonia on graphene-like B36 borophene: DFT studies

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Abstract

Ammonia N–H bond cleavage at metal-free substrates has attracted great attention because of its industrial importance. Here, we investigate the dissociative adsorption of ammonia onto the surface of a B36 borophene sheet by means of density functional theory calculations. We show that the N–H bond may be broken at the edges of B36 even at room temperature, regarding the small energy barrier of 14.1–19.3 kcal mol−1 at different levels of theory, and more negative Gibbs free energy change. Unlike basis set size, the kind of exchange correlation functional significantly affects the electronic properties of the studied systems. Also, by increasing the percentage of Hartree Fock (HF) exchange of density functionals, the activation and adsorption energies are lowered. A linear relationship between the highest occupied molecular orbital or lowest unoccupied molecular orbital of B36 borophene and the %HF exchange of functionals is predicted. Our work reveals that pure whole boron nanosheets may be promising metal-free materials in N–H bond cleavage, which would raise the potential application of these sheets.

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References

  1. Nakajima Y, Kameo H, Suzuki H (2006) Cleavage of nitrogen–hydrogen bonds of ammonia induced by triruthenium polyhydrido clusters. Angew Chem Int Ed 45(6):950–952

    Article  CAS  Google Scholar 

  2. Zhao J, Goldman AS, Hartwig JF (2005) Oxidative addition of ammonia to form a stable monomeric amido hydride complex. Science 307(5712):1080–1082

    Article  CAS  Google Scholar 

  3. Zhao J-X, Xiao B, Ding Y-H (2009) Theoretical prediction of the N−H and O−H bonds cleavage catalyzed by the single-walled silicon carbide nanotube. J Phys Chem C 113(38):16736–16740

    Article  CAS  Google Scholar 

  4. Moradi M, Peyghan AA, Bagheri Z, Kamfiroozi M (2012) Cation-π interaction of alkali metal ions with C24 fullerene: a DFT study. J Mol Model 18:3535–3540

    Article  CAS  Google Scholar 

  5. Beheshtian J, Baei MT, Peyghan AA, Bagheri Z (2012) Electronic sensor for sulfide dioxide based on AlN nanotubes: a computational study. J Mol Model 18:4745–4750

    Article  CAS  Google Scholar 

  6. Peyghan AA, Noei M, Tabar MB (2013) A large gap opening of graphene induced by the adsorption of Co on the Al-doped site. J Mol Model 19(8):3007–3014

    Article  CAS  Google Scholar 

  7. Ahmadi A, Beheshtian J, Kamfiroozi M (2012) Benchmarking of ONIOM method for the study of NH3 dissociation at open ends of BNNTs. J Mol Model 18(5):1729–1734

    Article  CAS  Google Scholar 

  8. Beheshtian J, Ahmadi Peyghan A, Bagheri Z (2013) Ab initio study of NH 3 and H 2 O adsorption on pristine and Na-doped MgO nanotubes. Struct Chem 24:165–170

    Article  CAS  Google Scholar 

  9. Beheshtian J, Peyghan AA, Bagheri Z (2012) Carbon nanotube functionalization with carboxylic derivatives: a DFT study. J Mol Model 19:391–396

    Article  Google Scholar 

  10. Soltani A, Ahmadi Peyghan A, Bagheri Z (2013) H2O2 adsorption on the BN and SiC nanotubes: a DFT study. Phys E 48:176–180

    Article  CAS  Google Scholar 

  11. Ahmadi A, Beheshtian J, Hadipour NL (2011) Chemisorption of NH3 at the open ends of boron nitride nanotubes: a DFT study. Struct Chem 22(1):183–188

    Article  CAS  Google Scholar 

  12. Pham HT, Duong LV, Tam NM, Pham-Ho MP, Nguyen MT (2014) The boron conundrum: bonding in the bowl B30 and B36, fullerene B40 and triple ring B42 clusters. Chem Phys Lett 608:295–302

    Article  CAS  Google Scholar 

  13. Li W-L, Chen Q, Tian W-J, Bai H, Zhao Y-F, Hu H-S, Li J, Zhai H-J, Li S-D, Wang L-S (2014) The B35 Cluster with a double-hexagonal vacancy: a new and more flexible structural motif for borophene. J Am Chem Soc 136(35):12257–12260

    Article  CAS  Google Scholar 

  14. Li W-L, Pal R, Piazza ZA, Zeng XC, Wang L-S (2015) B27−: Appearance of the smallest planar boron cluster containing a hexagonal vacancy. J Chem Phys 142(20):204305

    Article  Google Scholar 

  15. Piazza ZA, Hu H-S, Li W-L, Zhao Y-F, Li J, Wang L-S (2014) Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets. Nat Commun 5:3113–3117

    Article  Google Scholar 

  16. Chen Q, Wei G-F, Tian W-J, Bai H, Liu Z-P, Zhai H-J, Li S-D (2014) Quasi-planar aromatic B 36 and B 36− clusters: all-boron analogues of coronene. Phys Chem Chem Phys 16(34):18282–18287

    Article  CAS  Google Scholar 

  17. Liu C-S, Wang X, Ye X-J, Yan X, Zeng Z (2014) Curvature and ionization-induced reversible hydrogen storage in metalized hexagonal B36. J Chem Phys 141(19):194306

    Article  Google Scholar 

  18. Valadbeigi Y, Farrokhpour H, Tabrizchi M (2015) Adsorption of small gas molecules on B36 nanocluster. J Chem Sci 127(11):2029–2038

    Article  CAS  Google Scholar 

  19. Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799

    Article  CAS  Google Scholar 

  20. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S (1993) General atomic and molecular electronic structure system. J Comput Chem 14(11):1347–1363

    Article  CAS  Google Scholar 

  21. Politzer P, Murray JS (2002) The fundamental nature and role of the electrostatic potential in atoms and molecules. Theor Chem Accounts 108(3):134–142

    Article  CAS  Google Scholar 

  22. Politzer P, Murray JS (1991) Molecular electrostatic potentials and chemical reactivity. Rev Comput Chem 2:273–312

    Article  CAS  Google Scholar 

  23. Wiberg KB (1997) Properties of some condensed aromatic systems. J Org Chem 62(17):5720–5727

    Article  CAS  Google Scholar 

  24. Beheshtian J, Peyghan AA, Bagheri Z (2012) Detection of phosgene by Sc-doped BN nanotubes: a DFT study. Sensors Actuators B: Chem 171–172:846–852

    Article  Google Scholar 

  25. Ahmadi A, Hadipour NL, Kamfiroozi M, Bagheri Z (2012) Theoretical study of aluminum nitride nanotubes for chemical sensing of formaldehyde. Sensors Actuators B: Chem 161:1025–1029

    Article  CAS  Google Scholar 

  26. Peyghan AA, Hadipour NL, Bagheri Z (2013) Effects of Al doping and double-antisite defect on the adsorption of HCN on a BC2N nanotube: density functional theory studiess. J Phys Chem C 117(5):2427–2432

  27. Baei MT, Peyghan AA, Bagheri Z (2012) A computational study of AlN nanotube as an oxygen detector. Chin Chem Lett 23:965–968

    Article  CAS  Google Scholar 

  28. Baei MT, Peyghan AA, Bagheri Z, Tabar MB (2012) B-doping makes the carbon nanocones sensitive towards NO molecules. Phys Lett A 377:107–111

    Article  CAS  Google Scholar 

  29. Beheshtian J, Peyghan AA, Bagheri Z, Kamfiroozi M (2012) Interaction of small molecules (NO, H2, N2, and CH4) with BN nanocluster surface. Struct Chem 23:1567–1572

    Article  CAS  Google Scholar 

  30. Beheshtian J, Peyghan AA, Noei M (2013) Sensing behavior of Al and Si doped BC3 graphenes to formaldehyde. Sensors Actuators B: Chem 181:829–834

    Article  CAS  Google Scholar 

  31. 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(19):194101

    Article  Google Scholar 

  32. Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Accounts 120(1-3):215–241

    Article  CAS  Google Scholar 

  33. Zhao Y, Truhlar DG (2006) Density functional for spectroscopy: no long-range self-interaction error, good performance for Rydberg and charge-transfer states, and better performance on average than B3LYP for ground states. J Phys Chem A 110(49):13126–13130

    Article  CAS  Google Scholar 

  34. Peyghan AA, Noei M (2014) The alkali and alkaline earth metal doped ZnO nanotubes: DFT studies. Phys B Condens Matter 432:105–110

    Article  CAS  Google Scholar 

  35. Beheshtian J, Peyghan AA, Bagheri Z, Tabar MB (2013) Density-functional calculations of HCN adsorption on the pristine and Si-doped graphynes. Struct Chem 25:1–7

    Article  Google Scholar 

  36. Peyghan AA, Noei M (2014) Hydrogen fluoride on the pristine, Al and Si doped BC2N nanotubes: a computational study. Comput Mater Sci 82:197–201

    Article  CAS  Google Scholar 

  37. Beheshtian J, Peyghan AA, Bagheri Z (2013) Sensing behavior of Al-rich AlN nanotube toward hydrogen cyanide. J Mol Model 19(6):2197–2203

    Article  CAS  Google Scholar 

  38. Cohen AJ, Mori-Sánchez P, Yang W (2008) Insights into current limitations of density functional theory. Science 321(5890):792–794

    Article  CAS  Google Scholar 

  39. Peng C, Schlegel HB (1993) Combining synchronous transit and quasi-Newton methods to find transition states. Isr J Chem 33(4):449–454

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Payame Noor University (PNU), PO Box, 19395-3697, Tehran, Iran

    Zahra Rostami

  2. Young Researchers and Elite Club, Shahre-Rey Branch, Islamic Azad University, Tehran, Iran

    Hamed Soleymanabadi

Authors
  1. Zahra Rostami
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  2. Hamed Soleymanabadi
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Correspondence to Zahra Rostami.

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Rostami, Z., Soleymanabadi, H. N–H bond cleavage of ammonia on graphene-like B36 borophene: DFT studies. J Mol Model 22, 70 (2016). https://doi.org/10.1007/s00894-016-2954-8

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  • DOI: https://doi.org/10.1007/s00894-016-2954-8

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