Effect of n-Type Dopant Nitrogen in the Structure and Atomic Charges Distribution of Monolayer Graphene Sheet: A DFT Analysis

Anant Babu Marahatta

Abstract


Theoretical calculations are very powerful tool in the investigation of energetically most stable electronic structures and partial atomic charges distribution of the multi-atomic systems. Being one of the most important ab initio methods, two-dimensional (2D) periodic boundary condition (PBC) calculations of density functional theory (DFT) model are more specifically applicable while computing structures and properties of solid state multi-electron atomic or molecular systems. Present work is aimed at investigating and analyzing the effect of n-type dopant nitrogen in the ground state electronic structures and partial atomic charges distribution of the 2D monolayer graphene sheet by employing 2D PBC calculations of the DFT. At first, the 2D low energy unit cell structures of N-doped and undoped graphene sheets are produced separately and then confirmed hexagonal, honeycomb-like pattern of the carbon rings in their lattice. Interestingly, no significant distortions to the graphene lattice are observed while doping N atom (graphitic N-doping type). The inhomogeneous partial atomic charges in the terminal and nonterminal carbon atoms as well as a strong charge variation in the N and C atoms bonded to N are predicted by the Mulliken population analysis method. These theoretical achievements are not only important to speculate the most chemically "active-sites" in the N-doped and undoped monolayer graphene sheets, but also to justify increased capacitance of N-doped graphene materials. It is believed that present study would be very useful while functionalizing such 2D solid materials, means while tuning their physicochemical properties.   


Full Text:

PDF

References


Khyzhun, Y., Strunskus, T., Cramm, S., & Solonin, Yu. M. (2005). Electronic structure of CuWO4: XPS, XES and NEXAFS studies. Journal of Alloys and Compounds, 389:14-20.

Daudel, R. (1966). Electronic Structure of Molecules, Elsevier publication.

Gaussian 09 manual. http://gaussian.com/geom/?tabid=1#Geomkeyword ReadOptim izeoption

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A. , & Nakatsuji H., et al. (2004). Gaussian 09, Revision C.01, Gaussian, Inc.

Madan, R. D. (1997). Modern Inorganic Chemistry, S. Chand & Company.

McQuarrie, D. A., & Simon, J. D. (1998). Physical Chemistry: Molecular Approach, Viva Books.

Cohen, A. J., Sánchez, P. M., & Yang, W. (2008). Insights into Current Limitations of Density Functional Theory. Science 321:792-794.

Hohenberg, P., & Kohn, W. (1964). Inhomogeneous Electron Gas. Physical Review B 136: 864-871.

Kohn, W., & Sham, L. J. (1965) Self-Consistent Equations Including Exchange and Correlation Effects. Physical Review 140:A1133.

Shtepliuk, I., Caffrey, N. M., Iakimov, T., Khranovskyy, V., Abrikosov, I. A. & Yakimova, R. (2017). On the interaction of toxic heavy metals (Cd, Hg, Pb) with graphene quantum dots and infinite graphene. Scientific Report 7:3934–3950.

Tachikawa, H., Iyama, T., & Kawabata, H. (2014). Effect of hydrogenation on the band gap of graphene nano-flakes. Thin Solid Films 554:199-203.

Anota, E. C., Juarez, A. R., Castro, M., & Cocoletzi, H. H. (2013). A density functional theory analysis for the adsorption of the amine group on graphene and boron nitride nanosheets. Journal of molecular modeling 19:321-328.

Graphene: The Carbon-Based ‘Wonder Material’. https://www.compoundchem.com/ 2015 /06/23/ graphene/

Kelly, B. T. (1981). Physics of Graphite, Applied Science: London.

Dresselhaus, M. S., Dresselhaus, G., & Eklund, P. C. (1996). Science of Fullerenes and Carbon Nanotubes, Academic Press: San Diego.

Ni, Z. H., Wang, H. M., Kasim, J., Fan, H. M., Yu, T., Wu, Y. H., Feng, Y. P., & Shen, Z. X. (2007). Graphene Thickness Determination Using Reflection and Contrast Spectroscopy. Nano Letters 7:2758-2763.

Bundaleska, N., Henriques, J., Abrashev, M., Botelho do Rego, A. M., Ferraria, A. M., Almeida, A., Dias, F. M., Valcheva, E., Arnaudov, B., Upadhyay, K. K., Montemor, M. F., & Tatarova, E. (2018). Large-scale synthesis of free-standing N-doped graphene using microwave plasma, Scientific Reports 8:12595:1-10.

Tatarova, E., Bundaleska, N., Sarrette, J. Ph & Ferreira, C. M. (2014). Plasmas for environmental Issues: from hydrogen production to 2D materials assembly. Plasma Sources Science and Technology 23:063002.

Wang, X., Sun, G., Routh, P., Kim, D. H., Huang, W., & Chen, P. (2014). Heteroatom-doped graphene materials: syntheses, properties and applications. Chemical Society Reviews 43:7067-7098.

Wang, H., Maialagan, T. & Wang, X. (2012). Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catalysis 2:781–794.

Jafri, R. I., Rajalakshmi, N. & Ramaprabhu, S. (2010). Nitrogen doped graphene nanoplatelets as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell. Journal of Materials Chemistry 20:7114–7117.

Shao, Y., Zhang, S., Engelhard, M. H., Li, G., Shao, G., Wang, Y., Liu, J., Aksay, I. A., & Lin, Y. (2010). Nitrogen-doped graphene and its electrochemical applications. Journal of Materials Chemistry 20:7491–7496.

Du, D., Li, P. & Ouyang, J. (2015). Nitrogen-doped reduced graphene oxide prepared by simultaneous thermal reduction and nitrogen doping of graphene oxide in air and its application as an electrocatalyst. ACS Applied Materials & Interfaces 7:26952–26958.

Barrejón, M., Arellano, L. M., Gobeze, H. B., Gómez-Escalonilla M. J., Fierro, J. L. G., D'Souza, F., & Langa, F. (2018). N-Doped graphene/C60 covalent hybrid as a new material for energy harvesting applications. Chemical Science 9:8221-8227.

Marahatta, A. B. (2019). A DFT Analysis for the Electronic Structure, Mulliken Charges Distribution and Frontier Molecular Orbitals of Monolayer Graphene Sheet. International Journal of Progressive Sciences and Technologies 16(1):51-65.

Frisch, Æ., Hratchian, H. P., Dennington II, R. D., Keith, T. A., & Millam,J. (2009). Gauss view 5 Reference, Gaussian, Inc.

Xing, Z., Ju, Z., Zhao, Y., Wan, J., Zhu, Y., Qiang, Y., & Qian Y. (2016). One-pot hydrothermal synthesis of Nitrogen-doped graphene as high-performance anode materials for lithium ion batteries. Scientific Reports 6:26146:1-10.

Yagmurcukardes, M., Horzum, S., Torun, E., Nitrogenated, Peetersb, F. M., & Senger, T. R. (2016). Nitrogenated, phosphorated and arsenicated monolayer holey graphenes. Physical Chemistry Chemical Physics 18:3144-3150.

Cooper, D. R., Anjou, B. D., Ghattamaneni, N., Harack, B., Hilke, M., Horth, A., Majlis, N., Massicotte, M., Vandsburger, L., Whiteway, E., & Yu, V. (2011). Experimental review of graphene, McGill University.

Al-Muhit, B., & Sanchez, F. (2019). Tunable mechanical properties of graphene by clustered line pattern hydroxyl functionalization via molecular dynamics simulations. Carbon 146:680-700.

Islam, Md. M., Faisal, S. N., Roy, A. K., Ansari, S., Cardillo, D., Konstaninov, K., & Haque, E. (2015). Synthesis of Nitrogen-Doped Graphene via Thermal Treatment of Graphene Oxide within Methylimidazole and its Capacitance Performance as Electric Double Layer Capacitor. Journal of Nanotechnology and Materials Science 2(2):1-5.

R.S. Mulliken (1955). Mulliken populations. Journal of Chemical Physics 23, 1833-1841.

Li, J., Liu, G., Long, X., Gao, G., & Wu, J. (2017). Different active sites in a bifunctional Co @ N-doped graphene shells based catalyst for the oxidative dehydrogenation and hydrogenation reactions. Journal of Catalysis 355:53-62.

Li, J., Lin, L., Rui, D., Li, Q., Zhang, J., Kang, N., Zhang, Y., Pemg, H., Liu, Z., & Xu, H. Q. Electron-Hole Symmetry Breaking in Charge Transport in Nitrogen-Doped Graphene. https://export.arxiv.org/ftp/arxiv/papers/1705/1705.01429.pdf

Jalilian, R., Jauregui, L. A., Lopez, G., Tian, J., Roecker, C., Yazdanpanah, M. M., Cohn, R. W., Jovanovic I., & Chen, Y. P. (2011). Scanning gate microscopy on graphene: charge inhomogeneity and extrinsic doping. Nanotechnology 22:295705.

Miyamoto, Y., Nakada, K., & Fujita, M. (1999). First-principles study of edge states of H-terminated graphitic ribbons. Physical Review B 59:9858.

He, K., Lee, G. D., Robertson, A. W., Yoon, E., & Warner, J. H. (2014). Hydrogen-free graphene edges. Nature Communications 5:3040:1-7.

Weinhold, F., Landi, C. R., & Glendening, E. D. (2016). What is NBO analysis and how is it useful? International Reviews in Physical Chemistry 35(3):399-440.


Refbacks

  • There are currently no refbacks.


Copyright (c) 2019 Anant Babu Marahatta

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.