First-principles calculations of B/N co-doped graphene for sensing NO and NO2 molecules

https://doi.org/10.1016/j.physe.2019.05.002Get rights and content

Highlights

  • We reported a first-principles calculation of the interactions between NO, NO2 molecules and various graphene sheets, including 1B1N-doped graphene, 1B2N-doped graphene and 1N2B-doped graphene.

  • The adsorption sensitivity of 1N2B/G is lower than 1N1B/G and 1B2N/G to NO molecule.

  • The 1N1B/G is more suitable for the detection of NO2 molecule.

Abstract

Adsorption of NO and NO2 on the 1N1B/G, 1B2N/G and 1N2B/G are theoretically investigated using first-principles method based on density functional theory. The most stable adsorption geometry, adsorption energy, band structure and density of states of these systems are thoroughly discussed. It is found that NO molecule is weakly adsorbed on the 1N1B/G and 1B2N/G but their electronic properties are obviously changed. The adsorption sensitivity of 1N2B/G is lower than 1N1B/G and 1B2N/G to NO molecule. It is found that NO2 molecule is strongly adsorbed on the 1B2N/G but its electronic property is slightly changed. In contrast, the 1N1B/G is more suitable for the detection of NO2 molecule. The results will provide a new direction for the detection of NO and NO2 by introducing B and N doping atoms into graphene.

Introduction

Graphene, the current rage among carbonaceous materials, has attracted intense attentions since its experimental discovery in 2004 [[1], [2], [3]]. Graphene takes on fascinating physical and chemical properties [[3], [4], [5], [6], [7]] with applications in many areas, such as field-effect transistors [[8], [9], [10], [11]], solar cells [12], photovoltaics [13,14], gas sensors [15], super-capacitors [16,17] and so on.

Graphene is a two-dimensional Carbon materials, which has been research focus of nanomaterials science in the field of sensors since its discovery due to the physical and chemical properties. Compared with CNT, graphene has unusual transport and electronic properties along with high crystal qualities due to its unique zero band gap with linear and symmetric dispersion relation close to the Dirac points. So graphene-based nanostructures are considered to have a potential application in sensors of various types. However, most work focused on intrinsic graphene, and predicted relatively low adsorption energies in comparison with the essential requirement of gas sensing applications, mainly due to the inert property of perfect graphene. Recently, to overcome the insensitivity of graphene sheet to gas molecules, one may decorate the sheet with dopants, which can highly enhance the interaction between gas molecules and graphene substrate [[18], [19], [20]]. For graphene, B and N are the best candidates since they have similar covalent radius to C. The B and N atoms introduce holes and electrons to the lattice, leading to p- or n-type semiconductor nano-structure, respectively [21]. It is found that the B/N dopants in graphene sheets can modulate the chemical reactivity and the transport properties of the materials [[22], [23], [24], [25]]. Many researches on B/N-doped graphene have been carried out due to its promising applications, such as high electrocatalytic activity electrode materials, high on/off ratio field-effect transistors (FET) and energy storage application [[26], [27], [28], [29]].

Many experimental and theoretical research have shown that the doped graphene can be a promising candidate as sensing materials to detect different gas molecules [[30], [31], [32], [33], [34], [35]]. Herein, we focus on the small toxic gas molecules including NO and NO2. Dai investigated NO and NO2 adsorption on the B-, N- and S-doped graphenes by using the first-principles calculation in terms of electronic and adsorption properties [36]. It was found that the electronic properties of B-doped graphene are strongly sensitive to the presence of NO and NO2 molecules. Zhou reported the effects of Si doping on the interactions between graphene and five gas molecules (CO, H2O, NO, NO2, O2) and found that Si doping into the graphene could enhance the adsorption of NO, NO2 and O2 [37]. Zhang reported the effects of Stone-Wales defect on the interactions between graphene and NO2. It was found that NO2 showed weak interactions with perfect graphene, but observably enhanced the adsorption of NO2 [38]. These calculations show that the dopants can improve the adsorption properties so that the graphenes with dopants are strongly sensitive to the presence of NO and NO2 molecules. But, furthermore, we focus on the doping ratio of B atom and N atom in the graphene. In this study we show that how the different doping ratios of B and N change the adsorption properties of B/N-doped graphenes.

In this paper, we reported a first-principles calculation of the interactions between NO, NO2 molecules and various graphene sheets, including 1B1N-doped graphene (1B1N/G, B-to-N ratio is 1:1), 1B2N-doped graphene (1B2N/G, B-to-N ratio is 1:2) and 1N2B-doped graphene (1N2B/G, N-to-B ratio is 1:2). The most stable adsorption configuration, adsorption energy, band structures, and density of states (DOS) of the systems are analyzed and discussed. Such achievements have resulted in a good significance for guiding both the research on adsorption property of B/N-doped graphene and the researchers in their selection of doping ratio between B and N.

Section snippets

Theoretical method

The calculations are performed within the density functional theory (DFT) employing the Vienna Ab Initio Simulation Package (VASP) [39]. The electron-ion core interaction is described by the projector augmented wave (PAW) potentials [40]. To treat electron exchange and correlation, we chose the PBE [41] formulation of the generalized gradient approximation (GGA), which yields the correct ground state structure of the combined systems. In addition, we also use DFT-D3 [42] dispersion correction

The 1B1N-doped graphene

As shown in Fig. 1, we built models by placing NO and NO2 on three different high symmetry adsorption sites respectively, namely, T (the atom-top site, right above a B or N atom), B (bond-bridge site, right above the middle of a C–C bond), and H (hollow site, right above the center of the hexagonal).

At first, we investigated the most stable configuration of NO and NO2 adsorbed on the 1B1N-doped graphene. Three initial configurations (B, H, T) have been considered in order to find the most

Conclusions

Adsorption of NO and NO2 molecules on the 1N1B/G, 1B2N/G and 1N2B/G are investigated using DFT calculations. The electronic properties of the 1N1B/G and 1B2N/G are obviously changed upon the adsorption of NO molecule. In contrast, the adsorption sensitivity of 1N2B/G is lower than 1N1B/G and 1B2N/G to NO molecule. The presence of B and N impurities which have the doping ratio of one to one will make the adsorption of NO2 on graphene occur large change in the conductivity. It indicates that the

Acknowledgment

This work is supported by the Project of Hubei University of Arts and Science (No. XK2018030).

References (51)

  • C.H. Hu et al.

    Solid State Commun.

    (2011)
  • D.A.C. Brownson

    J. Power Sources

    (2011)
  • Y.N. Tang et al.

    Appl. Surf. Sci.

    (2014)
  • M. Oubal et al.

    Surf. Sci.

    (2010)
  • I. Lopez-Corral et al.

    Int. J. Hydrogen Energy

    (2012)
  • L.H. Yao et al.

    Comput. Mater. Sci.

    (2014)
  • G. Kresse et al.

    Comput. Mater. Sci.

    (1996)
  • M.D. Ganji

    Phys. Lett. A

    (2008)
  • M.D. Ganji et al.

    Appl. Surf. Sci.

    (2016)
  • A.K. Geim et al.

    Nat. Mater.

    (2007)
  • K.S. Novoselov et al.

    Science

    (2004)
  • J.D. Fowler et al.

    ACS Nano

    (2009)
  • F. Shen et al.

    Nanoscale

    (2013)
  • M.D. Stoller et al.

    Nano Lett.

    (2008)
  • T. Kuila et al.

    Nanoscale

    (2013)
  • B. Obradovic et al.

    Appl. Phys. Lett.

    (2006)
  • X. Liang et al.

    Nano Lett.

    (2007)
  • G. Fiori et al.

    IEEE Electron. Device Lett.

    (2007)
  • X. Wang et al.

    Phys. Rev. Lett.

    (2008)
  • X. Wang et al.

    Nano Lett.

    (2007)
  • C.A. Di et al.

    Adv. Mater.

    (2008)
  • H.A. Becerill et al.

    ACS Nano

    (2008)
  • I.I. Barbolina et al.

    Appl. Phys. Lett.

    (2006)
  • W. Choi et al.

    Crit. Rev. Solid State Mater. Sci.

    (2010)
  • J. Dai et al.

    Appl. Phys. Lett.

    (2009)
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