Skip to main navigation menu Skip to main content Skip to site footer


Vol. 7 (2020)

Theoretical Study Oxygen Reduction Activity of Phosphorus-doped Graphene Nanoribbons

March 27, 2020


Phosphorus-doped graphene is known to exhibit good electrocatalytic activity for oxygen reduction reaction (ORR). While the ORR activity of P-doped graphene nanoribbons (PGNR) is still unclear. Taking the common graphene nanoribbons with the edges of armchair as an example in this study, we research the mechanistic investigation of ORR on the PGNR under acidic electrolytic conditions by density functional theory (DFT). Based on the keen observation of the atomic charge distribution and adsorption energy at different sites, P atom in PGNR is considered to be the strongest adsorption site with oxygen. Detailed ORR mechanistic was deduced by the investigation of reaction heat, reaction barrier for each possible step and molecular dynamics (MD) simulation. Based on our calculations, when the contribution of the intermediate product to the ORR activity is not considered, PGNR does not possess the property as an ORR catalyst due to several high reaction barriers and some endothermic reactions for ORR path.


  1. I. Dincer, C. Acar, Review and evaluation of hydrogen production methods for better sustainability, Int. J. Hydrogen Energ. 40(34) (2015) 11094-11111.
  2. Y. Jiao, Y. Zheng, M. Jaroniec, S.Z. Qiao, Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions, Chem. Soc. Rev. 44(8) (2015) 2060- 2086.
  3. H.A. Gasteiger, N.M. Marković, Just a dream-or future reality?, Science 324(5923) (2009) 48-49.
  4. M. Shao, Q. Chang, J.P. Dodelet, R. Chenitz, Recent Advances in Electrocatalysts for Oxygen Reduction Reaction, Chem. Rev. 116(6) (2016) 3594-657.
  5. Y. Nie, L. Li, Z. Wei, Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction, Chem. Soc. Rev. 44(8) (2015) 2168-201.
  6. C. Hu, L. Dai, Doping of Carbon Materials for Metal-Free Electrocatalysis, Adv. Mater. 31(7) (2019) 1804672.
  7. Y. Jiao, Y. Zheng, M. Jaroniec, S.Z. Qiao, Origin of the Electrocatalytic Oxygen Reduction Activity of GrapheneBased Catalysts: A Roadmap to Achieve the Best Performance, J. Am. Chem. Soc. 136(11) (2014) 4394-4403.
  8. Y. Cheng, C. Xu, L. Jia, J.D. Gale, L. Zhang, C. Liu, P.K. Shen, S.P. Jiang, Pristine carbon nanotubes as non-metal electrocatalysts for oxygen evolution reaction of water splitting, Appl. Catal. B: Environ. 163 (2015) 96-104.
  9. M.D. Esrafili, E. Vessally, N2O + CO reaction over single Ga or Ge atom embedded graphene: A DFT study, Surf. Sci. 667 (2018) 105-111.
  10. J.Y. Cheon, J.H. Kim, J.H. Kim, K.C. Goddeti, J.Y. Park, S.H. Joo, Intrinsic relationship between enhanced oxygen reduction reaction activity and nanoscale work function of doped carbons, J. Am. Chem. Soc. 136(25) (2014) 8875-8.
  11. Z. Xie, M. Chen, S.G. Peera, C. Liu, H. Yang, X. Qi, U.P. Kumar, T. Liang, Theoretical Study on a Nitrogen-Doped Graphene Nanoribbon with Edge Defects as the Electrocatalyst for Oxygen Reduction Reaction, ACS Omega 5(10) (2020) 5142-5149.
  12. Z. Liang, M. Luo, M. Chen, C. Liu, S.G. Peera, X. Qi, J. Liu, U.P. Kumar, T.L.T. Liang, Evaluating the catalytic activity of transition metal dimers for the oxygen reduction reaction, J. Colloid Interf. Sci. 568 (2020) 54-62.
  13. S. Geng, J. Liu, C. Wang, L. Dong, T. Liang, Experimental analysis and theoretical studies by density functional theory of aminopropyl-modified ordered mesoporous carbon, Appl. Surf. Sci. 351 (2015) 911-919.
  14. J. Liu, C. Wang, L. Dong, T. Liang, Study on the Recycling of Nuclear Graphite after Micro-Oxidation, Nucl. Eng. Technol. 48(1) (2016) 182-188.
  15. L. Dai, Y. Xue, L. Qu, H.-J. Choi, J.-B. Baek, Metal-free catalysts for oxygen reduction reaction, Chem. Rev. 115(11) (2015) 4823-92.
  16. S.G. Peera, A.K. Sahu, A. Arunchander, S.D. Bhat, J. Karthikeyan, P. Murugan, Nitrogen and fluorine co-doped graphite nanofibers as high durable oxygen reduction catalyst in acidic media for polymer electrolyte fuel cells, Carbon 93 (2015) 130-142.
  17. S. Agnoli, M. Favaro, Doping graphene with boron: a review of synthesis methods, physicochemical characterization, and emerging applications, J. Mater. Chem. A 4(14) (2016) 5002- 5025.
  18. D.Y. Yeom, W. Jeon, N.D. Tu, S.Y. Yeo, S.S. Lee, B.J. Sung, H. Chang, J.A. Lim, H. Kim, High-concentration boron doping of graphene nanoplatelets by simple thermal annealing and their supercapacitive properties, Sci. Rep. 5 (2015) 9817.
  19. R. Vishwakarma, G. Kalita, S.M. Shinde, Y. Yaakob, C. Takahashi, M. Tanemura, Structure of nitrogen-doped graphene synthesized by combination of imidazole and melamine solid precursors, Mater. Lett. 177 (2016) 89-93.
  20. A. Arunchander, S.G. Peera, S.K. Panda, S. Chellammal, A.K. Sahu, Simultaneous co-doping of N and S by a facile insitu polymerization of 6-N,N-dibutylamine-1,3,5-triazine-2,4- dithiol on graphene framework: An efficient and durable oxygen reduction catalyst in alkaline medium, Carbon 118 (2017) 531-544.
  21. J. Wu, C. Jin, Z. Yang, J. Tian, R. Yang, Synthesis of phosphorus-doped carbon hollow spheres as efficient metalfree electrocatalysts for oxygen reduction, Carbon 82 (2015) 562-571.
  22. M. Klingele, C. Pham, K.R. Vuyyuru, B. Britton, S. Holdcroft, A. Fischer, S. Thiele, Sulfur doped reduced graphene oxide as metal-free catalyst for the oxygen reduction reaction in anion and proton exchange fuel cells, Electrochem. Commun. 77 (2017) 71-75.
  23. J.J. Spivey, K.S. Krishna, C.S.S.R. Kumar, K.M. Dooley, J.C. Flake, L.H. Haber, Y. Xu, M.J. Janik, S.B. Sinnott, Y.-T. Cheng, T. Liang, D.S. Sholl, T.A. Manz, U. Diebold, G.S. Parkinson, D.A. Bruce, P. de Jongh, Synthesis, Characterization, and Computation of Catalysts at the Center for Atomic-Level Catalyst Design, J. Phys. Chem. C 118(35) (2014) 20043-20069.
  24. S.H. Noh, C. Kwon, J. Hwang, T. Ohsaka, B.-J. Kim, T.-Y. Kim, Y.-G. Yoon, Z. Chen, M.H. Seo, B. Han, Self-assembled nitrogen-doped fullerenes and their catalysis for fuel cell and rechargeable metal–air battery applications, Nanoscale 9(22) (2017) 7373-7379.
  25. X. Hou, Q. Hu, P. Zhang, J. Mi, Oxygen reduction reaction on nitrogen-doped graphene nanoribbons: A density functional theory study, Chem. Phys. Lett. 663 (2016) 123-127.
  26. M.D. Esrafili, Nitrogen-doped (6,0) carbon nanotubes: A comparative DFT study based on surface reactivity descriptors, Comput. Theor. Chem. 1015(7) (2013) 1-7.
  27. L. Zhang, J. Niu, L. Dai, Z. Xia, Effect of Microstructure of Nitrogen-Doped Graphene on Oxygen Reduction Activity in Fuel Cells, Langmuir 28(19) (2012) 7542-7550.
  28. X.H. Zheng, L.F. Huang, X.L. Wang, J. Lan, Z. Zeng, Band gap engineering in armchair-edged graphene nanoribbons by edge dihydrogenation, Comp. Mater. Sci. 62 (2012) 93- 98.
  29. L. Zhang, Z. Xia, Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells, J. Phys. Chem. C 115(22) (2011) 11170-11176.
  30. Y. Wang, J. Mao, X. Meng, L. Yu, D. Deng, X. Bao, Catalysis with Two-Dimensional Materials Confining Single Atoms: Concept, Design, and Applications, Chem. Rev. 119(3) (2019) 1806-1854.
  31. K.V. Bets, B.I. Yakobson, Spontaneous Twist and Intrinsic Instabilities of Pristine Graphene Nanoribbons, Nano Res. 2(2) (2009) 161-166.
  32. H. Jin, C. Guo, X. Liu, J. Liu, A. Vasileff, Y. Jiao, Y. Zheng, S.Z. Qiao, Emerging Two-Dimensional Nanomaterials for Electrocatalysis, Chem. Rev. 118(13) (2018) 6337-6408.
  33. B. Delley, From molecules to solids with the DMol3 approach, J. Chem. Phys. 113(18) (2000) 7756-7764.
  34. B. Delley, An all-electron numerical method for solving the local density functional for polyatomic molecules, J. Chem. Phys. 92(1) (1990) 508-517.
  35. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77(18) (1996) 3865.
  36. S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, J. Comput. Chem. 27(15) (2006) 1787-99.
  37. A. Klamt, G. Schüürmann, COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient, J. Chem. Soc., Perkin Trans. 2 (5) (1993) 799-805.
  38. B. Delley, The conductor-like screening model for polymers and surfaces, Mol. Simulat. 32(2) (2006) 117-123.
  39. R.S. Mulliken, Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I, J. Chem. Phys. 23(10) (1955) 1833-1840.
  40. T. A.Halgren, W. N.Lipscomb, The synchronous-transit method for determining reaction pathways and locating molecular transition states, Chem. Phys. Lett. 49(2) (1997) 225-232.
  41. A. Sahu, G. Selvarani, S. Bhat, S. Pitchumani, P. Sridhar, A. Shukla, N. Narayanan, A. Banerjee, N. Chandrakumar, Effect of varying poly(styrene sulfonic acid) content in poly(vinyl alcohol)–poly(styrene sulfonic acid) blend membrane and its ramification in hydrogen–oxygen polymer electrolyte fuel cells, J. Membrane Sci. 319(1-2) (2008) 298-305.
  42. J.A. Keith, T. Jacob, Theoretical Studies of PotentialDependent and Competing Mechanisms of the Electrocatalytic Oxygen Reduction Reaction on Pt(111), Angew. Chem. Int. Ed. 49(49) (2010) 9521-9525.
  43. A.A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J.K. Nørskov, How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels, Energ. Environ. Sci. 3(9) (2010) 1311-1315.
  44. J.K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J.R. Kitchin, T. Bligaard, H. Jónsson, Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode, J. Phys. Chem. B 108(46) (2004) 17886-17892.
  45. H. Wang, H. Wang, Y. Chen, Y. Liu, J. Zhao, Q. Cai, X. Wang, Phosphorus-doped graphene and (8, 0) carbon nanotube: Structural, electronic, magnetic properties, and chemical reactivity, Appl. Surf. Sci. 273 (2013) 302-309.
  46. J. Dai, J. Yuan, Modulating the electronic and magnetic structures of P-doped graphene by molecule doping, J. Phys. Condens. Matt. 22(22) (2010) 225501.
  47. N. Yang, X. Zheng, L. Li, J. Li, Z. Wei, Influence of Phosphorus Configuration on Electronic Structure and Oxygen Reduction Reactions of Phosphorus-Doped Graphene, J. Phys. Chem. C 121(35) (2017) 19321-19328.
  48. E. Cruz-Silva, Z.M. Barnett, B.G. Sumpter, V. Meunier, Structural, magnetic, and transport properties of substitutionally doped graphene nanoribbons from first principles, Phys. Rev. B 83(15) (2011) 155445.
  49. Y. Ji, H. Dong, C. Liu, Y. Li, The progress of metal-free catalysts for the oxygen reduction reaction based on theoretical simulations, J. Mater. Chem. A 6(28) (2018) 13489-13508.
  50. L. Wang, H. Dong, Z. Guo, L. Zhang, T. Hou, Y. Li, Potential Application of Novel Boron-Doped Graphene Nanoribbon as Oxygen Reduction Reaction Catalyst, J. Phys. Chem. C 120(31) (2016) 17427-17434.
  51. X. Zhang, Z. Lu, Z. Fu, Y. Tang, D. Ma, Z. Yang, The mechanisms of oxygen reduction reaction on phosphorus doped graphene: A first-principles study, J. Power Sources 276 (2015) 222-229.
  52. B. He, J. Shen, D. Ma, Z. Lu, Z. Yang, Boron-Doped C3N Monolayer as a Promising Metal-Free Oxygen Reduction Reaction Catalyst: A Theoretical Insight, J. Phys. Chem. C 122(35) (2018) 20312-20322.
  53. Z. Liu, F. Peng, H. Wang, H. Yu, W. Zheng, X. Wei, Preparation of phosphorus-doped carbon nanospheres and their electrocatalytic performance for O2 reduction, J. Nat. Gas Chem. 21(3) (2012) 257-264.
  54. R. Li, Z. Wei, X. Gou, W. Xu, Phosphorus-doped graphene nanosheets as efficient metal-free oxygen reduction electrocatalysts, RSC Adv. 3(25) (2013) 9978.
  55. Z.W. Liu, F. Peng, H.J. Wang, H. Yu, W.X. Zheng, J. Yang, Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium, Angewandte Chemie 50(14) (2011) 3257-61.
  56. Y. Jiao, Y. Zheng, K. Davey, S.Z. Qiao, Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene, Nat. Energy 1(10) (2016) 16130.