Adsorption of nitrogen based gas molecules on noble metal functionalized carbon nitride nanosheets: A theoretical investigation

https://doi.org/10.1016/j.comptc.2020.112950Get rights and content

Highlights

  • The highest adsorption energy belongs to Pt adsorption on the C3N monolayer.

  • Pd and Pt-adsorbed systems exhibit semiconducting behavior, whereas Ag and Au-adsorbed ones represent metallic property.

  • NO2 molecule shows a stronger adsorption on the pristine and Pt-adsorbed C3N system.

Abstract

In this work, we have performed density functional theory calculations to examine the adsorption behaviors of some gas molecules (NO, N2O and NO2) on the carbon nitride (C3N) nanosheets adsorbed with transition metals (Au, Ag, Pd and Pt). Based on our calculated results, among the considered noble metals, the highest adsorption energy belongs to the adsorption of Pt atom on the C3N nanosheet, indicating the strong interaction between C3N and Pt adatom. The band structure diagrams show that Pt and Pd-adsorbed C3N nanosheets represent semiconductor property, while Au and Ag-adsorbed systems exhibit metallic character. The possible adsorption positions of NO, N2O and NO2 gas molecules on Pt-C3N nanosheets were also described. Besides, the considered gas molecules are chemisorbed on the Pt site of Pt-C3N nanosheets. The results obtained in this work suggest the Pt-functionalized C3N nanosheet as a favorable material for gas sensing in the environment.

Introduction

Motivated by the discovery of 2D graphene, marvelous efforts have been devoted to the fabrication, characterization, and theoretical investigation of a large variety of 2D nanostructures, including group IV-V buckled hexagonal layered materials, transition metal dichalcogenides, and so on [1], [2], [3], [4], [5], [6]. More recently, a two dimensional nanostructure composed of carbon and nitrogen atoms, C3N, has been successfully synthesized. C3N shows a semiconductor characteristics at room temperature with an indirect band gap and great carrier mobility, which makes it a promising candidate for application in optoelectronic and nanoscale devices [7].

Moreover, other 2D materials beyond graphene especially antimonene, bismuthene, C3N and other 2D systems have attracted enormous interests for their satisfied electronic band structures, making them efficient materials for optoelectronic applications [8], [9], [10], [11], [12], [13]. Furthermore, theoretical investigations have shown that the C3N nanosheet and its derivatives have excellent mechanical strength, appropriate band gap, and exceptional optical properties [14]. Field-effect transistors fabricated based on C3N monolayers exhibited a highly favorable current ratio [15]. Based on these findings, one can conclude that 2D semiconductors constructed from C3N sheets are favorable candidates for next-generation nanoelectronic and optoelectronic devices. From geometry point of view, perfect C3N has a planar honeycomb lattice with six C and two N atoms as in the case of 2 × 2 graphene supercell, which its two carbon atoms were replaced by nitrogen atoms. These two nitrogen atoms in the structure of C3N cause the higher activity of C3N monolayer in some fields such as heterostructure formation and gas sensing compared with the pristine graphene. Numerous strategies have been developed to modulate the electro-magnetic properties of 2D nanomaterials including substitutional elemental doping, defect engineering, adatoms functionalization, strain and electric field, and heterostructure formation [16], [17], [18], [19], [20], [21], [22], [23], [24].

Sensing air pollutants is of eminent importance for the indoor quality, environmental protection and medical treatment, and has fascinated fabulous interests because of the importance of toxic gas recognition in community healthiness. Thus, we have to suggest some appropriate materials, which are capable of detecting atmospheric toxic gases with enhanced sensitivity. In recent years, researchers have demonstrated that the novel electronic and magnetic properties can be introduced in 2D nanomaterials by efficient methods. For example, Bafekry et al. [25] examined the changes in the electronic properties and magnetic behaviors of C3N monolayers through defect engineering and substitution of atoms. Makaremi et al. [26] also suggested that the transition metals adsorption could improve the magnetic behavior of the C3N systems because of the main contribution of d orbitals in the electronic structures. Modulation of the sensing properties of C3N systems has also attracted great research interests in the past few years. Cui et al. [27] reported the results for the bigger selectivity and sensitivity of C3N monolayers towards sensing NO2 and SO2 molecules. Zhao et al. [28] proposed that the C3N nanosheet is a favorable candidate for NO2 detection in the environment.

In this work, we examined the electronic properties of noble metal (Pd, Pt, Ag and Au) adsorbed C3N nanosheets. The superior sensing performance of the Pt-adsorbed C3N system was also analyzed based on the results of adsorption energies and electronic structures. These findings would provide insights into the properties and performances of novel Pt-C3N systems to develop a new class of 2D modified nanosystems with extensive applications in future gas sensor devices.

Section snippets

Calculation methods and structures

The computations related to this study were conducted on the basis of density functional theory (DFT) [29], [30] as implemented in the electronic structure SIESTA package [31]. The Perdew–Burke–Ernzerhof (PBE) functional coupled with the generalized gradient approximation (GGA) was employed to describe the effects of exchange-correlation energy potential [32]. The convergence tolerances for the total energy and forces acting on each free atom in the system were set to 10-5 eV and 0.005 eV/Å,

Geometric stability and electronic properties of noble metal (Pd-Pt-Ag-Au) adsorbed C3N monolayers

To analyze the metal adsorption process, it is always worth noting that to scrutinize the electronic properties and structure of perfect C3N monolayer at the initial step. C3N monolayers have been emerged as an energetic analogues of graphene with intriguing electronic properties. In a simple 2 × 2 graphene supercell system containing eight carbon atoms, the substitution of two carbon atoms by N atoms gives rise to the construction of a new type of graphene-like materials, namely C3N. Thus, the

Conclusions

In conclusion, we have performed density functional theory computations to examine the relaxed geometries, electronic properties of noble metal (Pd-Pt-Ag-Au) adsorbed C3N monolayers. Our results showed that the adatoms were preferentially bound to the carbon centers of C3N. Pt atom has higher adsorption energy than the other adatoms, representing that Pt makes the strongest interaction with C3N monolayer. Pd and Pt do not change the semiconducting behavior of C3N and they exhibit an energy band

CRediT authorship contribution statement

Ziqi Yan: Conceptualization, Project administration, Methodology, Software, Validation. Chen Tao: Software, Investigation, Data curation, Writing - review & editing. Yu Bai: Visualization, Investigation, Writing - review & editing. Shupeng Liu: Software, Supervision, Project administration, Writing - original draft.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Shanghai Engineering Technology Research Centre of Deep Offshore Material (19DZ2253100).

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