A DFT-based analysis of adsorption properties of fluoride anion on intrinsic, B-doped, and Al-doped graphene


Fluorine emission from domestic wastewater is a major cause of severe environmental issues. In this paper, the density functional theory has been used to reveal the adsorption properties of F ions and HF molecules on intrinsic graphene, B-doped graphene, and Al-doped graphene. Throughout the analysis of band structure, geometric structure, adsorption energy, charge transfer, charge density, density of states, and frontier orbital, we can find that the adsorption of F ions and HF molecules on intrinsic graphene and HF molecules on B-doped graphene is weak, and it is only physical adsorption. When F ions and HF molecules are adsorbed on Al-doped graphene and F ions adsorbed on B-doped graphene, the adsorption energy, charge transfer, and charge density greatly increase, and the adsorption distance significantly decreases, and there exist obvious hybridizations by analyzing the charge density and density of states. We can also find that Al-doped graphene is more sensitive to F ions after comparing the variation of band gap. The work conducted in this research provides a theoretical guidance for the application of fluorine sensors based on graphene.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Data availability

All data generated or analyzed during this study are included in this published article.


  1. 1.

    Fuge R (2019) Fluorine in the environment, a review of its sources and geochemistry. Appl. Geochem. 100:393–406

    CAS  Article  Google Scholar 

  2. 2.

    J. Yang, M. Wang, J. Lu, K. Yang, K. Wang, M. Liu, H. Luo, L. Pang, B. Wang, Fluorine in the environment in an endemic fluorosis area in southwest, China.  Environmental Research 184 (2020) 109300

  3. 3.

    Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J. Environ. Manag. 92:407–418

    CAS  Article  Google Scholar 

  4. 4.

    Wang Q, Yang Z (2016) Industrial water pollution, water environment treatment, and health risks in China. Environ. Pollut. 218:358–365

    CAS  Article  Google Scholar 

  5. 5.

    Fiyadh SS, AlSaadi MA, Jaafar WZ, AlOmar MK, Fayaed SS, Mohd NS, Hin LS, El-Shafie A (2019) Review on heavy metal adsorption processes by carbon nanotubes. J. Clean. Prod. 230:783–793

    CAS  Article  Google Scholar 

  6. 6.

    Babel S, Kurniawan TA (2003) Low-cost adsorbents for heavy metals uptake from contaminated water: a review. J. Hazard. Mater. 97:219–243

    CAS  Article  Google Scholar 

  7. 7.

    Ali I, Gupta VK (2006) Advances in water treatment by adsorption technology. Nat. Protoc. 1:2661–2667

    CAS  Article  Google Scholar 

  8. 8.

    Novoselov K, Geim A, Morozov S, Jiang D, Zhang Y, Dubonos S, Grigorieva I, Firsov A (2004) Discover of graphene: electric field effect in atomically thin carbon films. Science 306:666–669

    CAS  Article  Google Scholar 

  9. 9.

    Jia X, Zhang H, Zhang Z, An L (2019) First-principles investigation of vacancy-defected graphene and Mn-doped graphene towards adsorption of H2S. Superlattice. Microst. 134:106235

    CAS  Article  Google Scholar 

  10. 10.

    Cui T, Mukherjee S, Cao C, Sudeep PM, Tam J, Ajayan PM, Singh CV, Sun Y, Filleter T (2018) Effect of lattice stacking orientation and local thickness variation on the mechanical behavior of few layer graphene oxide. Carbon 136:168–175

    CAS  Article  Google Scholar 

  11. 11.

    Bulat FA, Burgess JS, Matis BR, Baldwin JW, Macaveiu L, Murray JS, Politzer P (2012) Hydrogenation and fluorination of graphene models: analysis via the average local ionization energy. J. Phys. Chem. A 116:8644–8652

    CAS  Article  Google Scholar 

  12. 12.

    Gallouze M, Kellou A, Drir M (2016) Adsorption isotherms of H2 on defected graphene: DFT and Monte Carlo studies. Int. J. Hydrog. Energy 41:5522–5530

    CAS  Article  Google Scholar 

  13. 13.

    Li Y, Li K, Sun X, Song X, Sun H, Ning P (2019) DFT calculation of AsH3 adsorption and dissociation on Ni- and Cu-doped graphene. J. Mol. Model. 25:358

    CAS  Article  Google Scholar 

  14. 14.

    Zhang X, Xia Z, Li H, Yu S, Wang S, Sun GS (2019) The mechanism and activity of oxygen reduction reaction on single atom doped graphene: a DFT method. RSC Adv. 9:7086–7093

    CAS  Article  Google Scholar 

  15. 15.

    Murray JS, Shields ZP, Lane P, Macaveiu L, Bulat FA (2013) The average local ionization energy as a tool for identifying reactive sites on defect-containing model graphene systems. J. Mol. Model. 19:2825–2833

    CAS  Article  Google Scholar 

  16. 16.

    Montejo-Alvaro F, Oliva J, Herrera-Trejo M, Hdz-Garcí HM, Mtz-Enriquez AI (2019) DFT study of small gas molecules adsorbed on undoped and N-, Si-, B-, and Al-doped graphene quantum dots. Theor. Chem. Accounts 138:37

    Article  Google Scholar 

  17. 17.

    Rad A (2016) Al-doped graphene as a new nanostructure adsorbent for some halomethane compounds: DFT calculations. Surf. Sci. 645:6–12

    CAS  Article  Google Scholar 

  18. 18.

    Jia X, An L, Chen T (2020) Adsorption of nitrogen oxides on Al-doped carbon nanotubes: the first principles study. Adsorption 26:587–595

    CAS  Article  Google Scholar 

  19. 19.

    M.T. Jin, L.C. Yu, W.M. Shi, J.G. Deng, Y.N. Zhang, Enhanced absorption and diffusion properties of lithium on B, N, V-C-decorated graphene. Scientific Reports, 6 (2016) 37911

  20. 20.

    Jia X, An L (2019) The adsorption of nitrogen oxides on noble metal-doped graphene: the first-principles study. Modern Physical Letter B 33:1950044

    Article  Google Scholar 

  21. 21.

    Peyghan A, Noei M, Yourdkhani S (2013) Al-doped graphene-like BN nanosheet as a sensor for para-nitrophenol: DFT study. Superlattice. Microst. 59:115–122

    CAS  Article  Google Scholar 

  22. 22.

    Lv R, Li Q, Botello-Méndez AR, Hayashi T, Wang B, Berkdemir A, Hao Q, Eléas AL, Cruz-Silva R, Gutiérrez HR, Kim YA, Muramatsu H, Zhu J, Endo M, Terrones H, Charlier JC, Pan M, Terrones M (2012) Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing. Sci. Rep. 2:1–8

    Article  Google Scholar 

  23. 23.

    Ketabi N, Boer T, Karakaya M, Zhu J, Podila R, Rao AM, Kurmaev EZ, Moewes A (2016) Tuning the electronic structure of graphene through nitrogen doping: experiment and theory. RSC Advance 6:56721–56727

    CAS  Article  Google Scholar 

  24. 24.

    Lv R, Chen G, Li Q, McCreary A, Botello-Méndez A, Morozov SV, Liang L, Declerck X, Perea-López N, Cullen DA, Feng S, Elías AL, Cruz-Silva R, Fujisawa K, Endo M, Kang F, Charlier JC, Meunier V, Pan M, Harutyunyan AR, Novoselov KS, Terrones M (2015) Ultrasensitive gas detection of large-area boron-doped graphene. Proc. Natl. Acad. Sci. 112:14527–14532

    CAS  Article  Google Scholar 

  25. 25.

    Liu Y, An L, Gong L (2018) First-principles study of Cu adsorption on vacancy-defected/Au-doped graphene. Modern Physics Letters B 32:1850139

    CAS  Article  Google Scholar 

  26. 26.

    Liu Y, Zhang H, Zhang Z, Jia X, An L (2019) Co adsorption on Fe-doped vacancy-defected CNTs–A DFT study. Chem. Phys. Lett. 730:316–320

    CAS  Article  Google Scholar 

  27. 27.

    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys. Rev. Lett. 77:3865–3868

    CAS  Article  Google Scholar 

  28. 28.

    Klamt A (2016) COSMO-RS for aqueous solvation and interfaces. Fluid Phase Equilib. 407:152–158

    CAS  Article  Google Scholar 

  29. 29.

    Constantin LA, Perdew JP, Tao J (2006) Meta-generalized gradient approximation for the exchange-correlation hole with an application to the jellium surface energy. Phys. Rev. B 73:5104–5109

    Article  Google Scholar 

  30. 30.

    Meyer JC, Geim AK, Katsnelson MI, Novoselov KS, Booth TJ, Roth S (2007) The structure of suspended graphene sheets. Nature 446:60–63

    CAS  Article  Google Scholar 

  31. 31.

    Bardarson JH, Tworzydło J, Brouwer PW, Beenakker CWJ (2007) One-parameter scaling at the Dirac point in graphene. Phys. Rev. Lett. 99:106801

    CAS  Article  Google Scholar 

  32. 32.

    Jensen A, Strange M, Smidstrup S, Stokbro K, Solomon GC, Reuter MG (2017) Complex band structure and electronic transmission. J. Chem. Phys. 142:224104

    Article  Google Scholar 

  33. 33.

    Ishikawa M, Ikuta S, Katada M, Sano H (1990) Anisotropy of Van Der Waals radii of atoms in molecules: alkali-metal and halogen atoms. Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials 46:592–598

    Article  Google Scholar 

  34. 34.

    Clark T, Murray JS, Politzer P (2018) A perspective on quantum mechanics and chemical concepts in describing noncovalent interactions. Phys. Chem. Chem. Phys. 20:30076

    CAS  Article  Google Scholar 

  35. 35.

    Li W, Lu X, Li G, Ma J, Zeng P, Chen J, Pan Z, He Q (2016) First-principle study of SO2 molecule adsorption on Ni-doped vacancy-defected single-walled (8,0) carbon nanotubes. Appl. Surf. Sci. 364:560–566

    CAS  Article  Google Scholar 

  36. 36.

    Geim AK, Novoselov KS (2007) The rise of graphene. Nature Material 6:183–191

    CAS  Article  Google Scholar 

  37. 37.

    Madkour LH (2014) Correlation between corrosion inhibitive effect and quantum molecular structure of Schiff bases for iron in acidic and alkaline media. Nature 2:680–704

    Google Scholar 

  38. 38.

    Wang K, Shi C, Zhao N, Du X (2008) First-principle study of the effect of boron (nitrogen)-doping on adsorbing characteristics of aluminum on single-walled carbon nanotubes. Acta Phys. Sin. 57:7833–7840

    CAS  Google Scholar 

Download references


The authors received support from The National Natural Science Foundation of China (Grant No. 51472074).

Author information




Tao Chen conducted investigation, methodology, data curation and analysis, visualization, and original draft writing. Libao An conducted conceptualization, funding acquisition, supervision, and final approval of the version to be published. Xiaotong Jia conducted validation and interpretation of data, writing-reviewing, and editing.

Corresponding author

Correspondence to Libao An.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Chen, T., An, L. & Jia, X. A DFT-based analysis of adsorption properties of fluoride anion on intrinsic, B-doped, and Al-doped graphene. J Mol Model 27, 56 (2021). https://doi.org/10.1007/s00894-021-04683-7

Download citation


  • Doped graphene
  • Fluorine
  • Adsorption
  • DFT
  • Wastewater treatment