Document Type : Original Paper


1 Department of Chemistry, Shahr-e Qods branch, Islamic Azad University, Tehran, Iran

2 Department of chemistry, Payame Noor University, P.O.Box:19395-3697 Tehran, Iran


In this study, density functional theory was used to investigate the effect of adsorption process and interaction between methanol as a fuel and graphene as a catalyst. Thermodynamic studies in this field have shown that Gibb's free energy is positive in most cases. Therefore, adsorption of methanol on graphene is very low and in the physical mode. Thus, other ways are required to increase adsorption on graphene surface. Changing pristine graphene (PG) to vacancy graphene (VG) or N-doped graphene (NG) can increase absorption, and convert their adsorption into chemical adsorption. Vacancy and N-doped in electronic structure of graphene increase adsorption of methanol to graphene. Increased absorption of VG and NG, in addition to changes in charge transfer causes significant changes in the location of HOMO and LUMO, which was confirmed by adsorption energy, NBO, QTAIM, and DOS.


1.   Schröder E. Methanol Adsorption on Graphene. J Nanomater. 2013;13:1303-3774.
2.   Elfasakhany A. Performance and emissions of spark-ignition engine using ethanol–methanol–gasoline, n-butanol–iso-butanol–gasoline and iso-butanol–ethanol–gasoline blends: a comparative study. Int J Eng Sci Technol. 2016;19(4):2053-9.
3.   Bata RM, Roan VP. Effects of Ethanol and/or Methanol in Alcohol-Gasoline Blends on Exhaust Emissions. J Eng Gas Turbines Power. 1989;111(3):432-8.
4.   BahattinÇelik M, Özdalyan B, Alkan F. The use of pure methanol as fuel at high compression ratio in a single cylinder gasoline engine. Fuel. 2011;90(4):1591-8.
5.   Wang X, Ge Y, Liu L, Peng Z, Hao L, Yin H, et al. Evaluation on toxic reduction and fuel economy of a gasoline direct injection- (GDI-) powered passenger car fueled with methanol–gasoline blends with various substitution ratios. Appl Energy. 2015;157:134-43.
6.   Zhang Z, Cheung C, Chan T, Yao C. Emission reduction from diesel engine using fumigation methanol and diesel oxidation catalyst. Science of the Total Environment. 2009;407(15):4497-505.
7.   Stankovich S, Dikin DA, Dommett GH, Kohlhaas KM, Zimney EJ, Stach EA, et al. Graphene-based composite materials. nature. 2006;442(7100):282-6.
8.   Huang X, Qi X, Boey F, Zhang H. Graphene-based composites. Chem Soc Rev. 2012;41(2):666-86.
9.   Xu X, Zhou Y, Yuan T, Li Y. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea. Electrochim Acta. 2013;112:587-95.
10. Zhang L-S, Liang X-Q, Song W-G, Wu Z-Y. Identification of the nitrogen species on N-doped graphene layers and Pt/NG composite catalyst for direct methanol fuel cell. Phys Chem Chem Phys. 2010;12(38):12055-9.
11. Jia X, Zhang H, Zhang Z, An L. Effect of doping and vacancy defects on the adsorption of CO on graphene. Materials Chemistry and Physics. 2020;249:123114.
12. Zhu X, Zhang L, Zhang M, Ma C. Effect of N-doping on NO2 adsorption and reduction over activated carbon: An experimental and computational study. Fuel (Guildford). 2019;258:116109.
13. Dong L, Gari RRS, Li Z, Craig MM, Hou S. Graphene-supported platinum and platinum–ruthenium nanoparticles with high electrocatalytic activity for methanol and ethanol oxidation. Carbon. 2010;48(3):781-7.
14. Rad AS. Density functional theory study of the adsorption of MeOH and EtOH on the surface of Pt-decorated graphene. Physica E: Low-dimensional Systems and Nanostructures. 2016;83:135-40.
15. Kiyani R, Rowshanzamir S, Parnian MJ. Nitrogen doped graphene supported palladium-cobalt as a promising catalyst for methanol oxidation reaction: Synthesis, characterization and electrocatalytic performance. Energy. 2016;113:1162-73.
16. Lv R, Terrones M. Towards new graphene materials: Doped graphene sheets and nanoribbons. Mater Lett. 2012;78:209-18.
17. Zhao XW, Tian YL, Yue WW, Chen MN, Hu GC, Ren JF, et al. Adsorption of methanol molecule on graphene: Experimental results and first-principles calculations. Int J Mod Phys B. 2018;32(09):1850102.
18. Wang H, Maiyalagan T, Wang X. Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications. ACS Catalysis. 2012;2(5):781-94.
19. Doronin M, Bertin M, Michaut X, Philippe L, Fillion J-H. Adsorption energies and prefactor determination for CH3OH adsorption on graphite. J Chem Phys. 2015;143:084703.
20. Xu X, Zhou Y, Lu J, Tian X, Zhu H, Liu J. Single-step synthesis of PtRu/N-doped graphene for methanol electrocatalytic oxidation. Electrochim Acta. 2014;120:439-51.
21. Becke AD. Density‐functional thermochemistry. III. The role of exact exchange. J Chem Phys. 1993;98(7):5648-52.
22. Calais J-L. Density-functional theory of atoms and molecules. R.G. Parr and W. Yang, Oxford University Press, New York, Oxford, 1989. IX + 333 pp. Price £45.00. Int J Quantum Chem. 1993;47(1):101-.
23. Lee C, Yang W, Parr RG. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B. 1988;37(2):785-9.
24. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, G09. Exp limit comput chem 2009.
25. ShokuhiRad A, Shabestari SS, Jafari SA, Zardoost MR, Mirabi A. N-doped graphene as a nanostructure adsorbent for carbon monoxide: DFT calculations. Molecular Physics. 2016;114(11):1756-62.
26. Chattaraj PK, Sarkar U, Roy DR. Electrophilicity Index. Chem Rev. 2006;106(6):2065-91.
27. Morrison RC. The extended Koopmans’ theorem and its exactness. The Journal of Chemical Physics. 1992;96(5 ):10.1063/1.461875.
28. Parr RG, Szentpály Lv, Liu S. Electrophilicity Index. Journal of the American Chemical Society. 1999;121(9):1922-4.
29. Liu G-H, Parr RG. On Atomic and Orbital Electronegativities and Hardnesses. J Am Chem Soc. 1995;117(11):3179-88.
30. Raju HB, Goldberg JL. Nanotechnology for ocular therapeutics and tissue repair. Expert Review of Ophthalmology. 2008;3(4):431-6.
31. Shao Y, Wang J, Wu H, Liu J, Aksay IA, Lin Y. Graphene Based Electrochemical Sensors and Biosensors: A Review. Electroanalysis. 2010;22(10):1027-36.
32. Marcou G, Flamme B, Beck G, Chagnes A, Mokshyna O, Horvath D, et al. In silico Design, Virtual Screening and Synthesis of Novel Electrolytic Solvents. Molecular Informatics. 2019;38(10):1900014.
33. Rozas I, Alkorta I, Elguero J. Behavior of Ylides Containing N, O, and C Atoms as Hydrogen Bond Acceptors. J Am Chem Soc. 2000;122(45):11154-61.
34. Politzer P, Murray JS. Quantitative Analyses of Molecular Surface Electrostatic Potentials in Relation to Hydrogen Bonding and Co-Crystallization. Cryst Growth Des. 2015;15(8):3767-74.
35. Esfandfard SM, Elahifard M, Behjatmanesh-Ardakanii R, Kargar H. DFT study on oxygen-vacancy stability in rutile/anatase TiO2: Effect of cationic substitutions. Physical Chemistry Research. 2018;6:547-63.
36. Khosravi A, Vessally E, Oftadeh M, Behjatmanesh-Ardakani R. Ammonia capture by MN4 (M = Fe and Ni) clusters embedded in graphene. Journal of Coordination Chemistry. 2018;71(21):3476-86.
37. O'Boyle N, Tenderholt A, Langner K. cclib: A Library for Package-Independent Computational Chemistry Algorithms. J Comput Chem. 2008;29(5):839-45.
38. Bader RFW. Atoms in Molecules: A Quantum Theory (International Series of Monographs on Chemistry (22)). Science & Math. 1994;22:458.
39. Padmanabhan J, Parthasarathi R, Elango M, Subramanian V, Krishnamoorthy BS, Gutierrez-Oliva S, et al. Multiphilic Descriptor for Chemical Reactivity and Selectivity. J Phys Chem A. 2007;111(37):9130-8.
40. Islam DN, Ghosh D. On the Electrophilic Character of Molecules Through Its Relation with Electronegativity and Chemical Hardness. Int J Mol Sci. 2012;13:2160-75.
41. Weinhold F, Landis CR. NATURAL BOND ORBITALS AND EXTENSIONS OF LOCALIZED BONDING CONCEPTS. Chemistry Education Research and Practice. 2001;2(2):91-104.
42. Ziolkowski M, Grabowski SJ, Leszczynski J. Cooperativity in hydrogen-bonded interactions: ab initio and "atoms in molecules" analyses. J Phys Chem A. 2006;110(20):6514-21.