Vinyl chloride adsorption onto the surface of pristine, Al-, and Ga-doped boron nitride nanotube: A DFT study

https://doi.org/10.1016/j.ssc.2021.114440Get rights and content

Highlights

  • The interaction of VCM with BNNT, BNAlNT, and BNGaNT are studied.

  • To study the adsorption processes, the results of an NBO analysis are analyzed.

  • To unravel the nature of intermolecular interactions a QTAIM analysis is applied.

  • NCI analysis were performed to consider the non-covalent interactions.

Abstract

The density functional techniques (DFT) were put into practice to study the nature of the intermolecular interactions between Vinyl chloride (VCM) gas molecule with single-walled pristine, Al and Ga-doped boron nitride nanotubes (BNNT, BNAlNT, and BNGaNT, respectively). For performing optimization process, various functionals including PBE0, M06–2X, ωB97XD, and B3LYP-D3 were applied on both of the isolated and complex structures. All of the functionals were used together with split-valence triple-zeta basis sets with d-type Cartesian-Gaussian polarization functions (6-311G(d)). To consider the electronic structure, total density of state (DOS) analysis were employed. Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), and non-covalent interaction (NCI) analyses were also taken on board to discover the nature of intermolecular interactions between gas and nanotubes. The results of electronic structure calculations as well as population analyses has been carefully tabulated and partially depicted. The HOMO-LUMO energy gap (HLG) were dramatically changed when the dopant atom added to the BNNT. It means the impurity can improve the sensivity and reactivity of the pristine nanotube; therefore, by absorbing the VCM onto the surface of the titled nanotubes, a salient signal can produce in a typical electronic circuit. Among all of the absorbents, BNGaNT shows the most favorable material to design a nanosensor for the studied gas molecule.

Introduction

After the emergence of density functional theory (DFT) due to its high computational power for large molecules as well as its considerable accuracy and speed, a suitable framework was provided for the theoretical studies of chemical systems. Many scientists today use this method to understand the properties of chemical structures. Meanwhile, theoretical studies on nanoscale structures have found an extraordinary place in computational chemistry, and researchers have used numerous computational methods to study intermolecular interactions to design tools that have better accuracy and performance [[1], [2], [3], [4], [5]]. A variety of nanomaterials have been considered for the construction of sensors with high measurement accuracy, extreme insensitivity to temperature, very low response time, low production costs, and resistant to harsh environmental conditions [[6], [7], [8], [9], [10], [11], [12]].

Different of methods have been used in theoretical studies to improve the sensitivity of the adsorption process in nanomaterials such as metal doping [[13], [14], [15]], surface defect [[16], [17], [18]], transition metal decoration [19,20], etc. Impurities introduced to the nanomaterial wall change the energy gap, and also dramatically change its morphology. Lin et al. provides a comprehensive study on the effect of transition metal decoration to boron nitride nanotube [21]. Studies have shown that even the introduction of non-metals such as oxygen can activate the surface of nanomaterials [22]. Demonstrating the benefits of dopant element, we can point out that by reducing the electrical resistance, impurity-decorated nanomaterials can generate a stronger signal in the circuit. Therefore, compared to pure nanomaterials, it can be said that decorated nanomaterials have a higher efficiency [23]. Aluminum and gallium and germanium are the elements that have been widely used to activate the surface of nanotubes in theoretical studies [[24], [25], [26], [27]].

Following the discovery of boron nitride nanotubes in 1994 by Rubio et al. [28] and its synthesis by Chopra et al., In 1995 [29,30], Deca et al., Interactions between (10,0) and (10, 5) nanotubes 5) reported with the drug molecule isoniazid (INH); they showed that the binding energy of INH to BNNT (5,5) was slightly more significant than BNNT (10,0) [31]. Mukhopadhyay et al. Showed that by adsorption of tryptophan (non-polar amino acid), sparic acid and arginine (polar amino acid) on BNNTs, a strong bonding energy between polar amino acids on the surface of boron nitride nanotubes is being observed [32]. Peyghan et al. investigated the absorption and electrical structure of BNNT (6.0) imidazole molecule in gaseous and soluble phases. They found that imidazole adsorption had no significant effect on the electrical structure of BNNT [33]. Yang et al. performed the interaction between BNNTs with biological molecules using DFT calculations [34]. Anota et al. investigated the interaction between BNNT and metformin using DFT methods [35]. Recently, the interaction between the uracil molecule with BNNT (n, 0) has been investigated by Mirzai et al. [36]. After the widespread use of boron nitride nanotube, there are lots of theoretical investigation on the adsorption of different molecules onto the surface of different nanostructures like aluminun nitride, silicon carbid, etc [5,[10], [11], [12],[37], [38], [39], [40]].

This article encompasses a comprehensive study to investigate the intermolecular interactions of the VCM gas molecule with pristine BNNT plus nanotubes doped with Al and Ga elements. The details information about the computational level was given in section 2. The result and discussion section has been divided in 4 separate subsections: Geometric Surveys (3.1.), which provides insights about bond length and other geometry properties as well as introducing the levels of study for optimizing all structures; Electronic Structure (3.2.) that discusses about DOS and energetic properties results; NBO analysis (3.3.) and QTAIM analysis (3.4) are provided to show the nature of intermolecular interactions between two fragments. We tried to provide a brief theory for each part using useful references and avoided to bring boring description. And finally, the conclusion section briefly refers to all the findings in this study.

Section snippets

Computational details

The PBE0 functional together with 6-311G(d) basis set were selected at the first stage to start the geometry optimization process of the isolated and complex structures. All of the structures were re-optimized using robust methods like M06–2X, ωB97XD, and B3LYP-D3. Head-Gordon et al. [41] invented the ωB97XD functional to account for the effect of long-range interactions as well as the dispersion corrections. Among Minnesota 06 suit, which is developed by Truhlar et al. [42], the global hybrid

Conclusion

The intermolecular interactions between the VCM gas molecule and BNNT, BNAlNT, and BNGaNT were studied by the DFT framework in vacuum condition. All molecular structures optimized at PBE0, ωB97XD, M06–2X, and B3LYP-D3 functionals together wit a 6-311G(d) basis set. Relaxed structures obtained from ωB97XD/6-311G(d) were chosen for population analysis calculations. Results of adsorption energy show that among the nanotubes, the interaction of BNGaNT and gas (about −0.843 eV) is higher than the

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

I would like to thank the Solid-State Theory Group at the Physics Department at the Universita’ degli Studi di Milano-Italy for providing computational facilities.

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