The adsorption of bromochlorodifluoromethane on pristine, Al, Ga, P, and As-doped boron nitride nanotubes: A study involving PBC-DFT, NBO analysis, and QTAIM

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Highlights

  • The adsorption of CBrClF2 on to the BNNT, BNAlNT, BNGaNT, BNPNT, and BNAsNT are studied.

  • To investigare the adsorption processes, the results of an NBO and QTAIM analyses are analyzed.

  • To find out the nature of intermolecular interactions aRDG diagrams are depicted.

Abstract

Nanostructures such as nanotubes and nanosheets are widely used in the medical industry for drug delivery, prevention, and treatment. These nanostructures are used as sensors or carriers by adsorbing functional groups. In this study, the adsorption rates of the bromochlorodifluoromethane (CBrClF2) molecule, which is used as an effective gaseous fire suppression agent, onto the outer surfaces of pristine, Al, Ga, P, and As-doped boron nitride nanotubes are investigated. A periodic boundary condition density functional theory method using both Perdew, Burke, and Ernzerhof exchange–correlation (PBEPBE) and B3LYP-D3 functionals together with the 6-311G (d) basis set were used. Subsequently, the B3LYP, CAM-B3LYP, ωB97XD, and M06-2X functionals with the 6-311G (d) basis set were used to consider the single-point energies. Natural bond orbital analysis and the quantum theory of atoms in molecule were considered using the PBEPBE/6-311G (d) method, and the results were compatible with the expected electronic properties, namely the Wiberg bond index, natural charge, natural electron configuration, donor–acceptor natural bond orbital interactions, and second-order perturbation energies. All the calculations and analyses denoted that the adsorption of the CBrClF2 molecule onto the surfaces of pristine boron nitride nanotubes occurred due to physical adsorption and van der Waals interactions. Among the doped nanotubes, the Al nanotube exhibited the highest adsorption energy compared to the other doped nanotubes.

Introduction

Nanotubes are structurally divided into carbon and non-carbon nanotubes. Carbon nanotubes (CNTs) were first discovered independently by Iijima and Ichihashi in 1991 in soot from carbon discharge in a neon-containing medium [1]. CNTs can pass through cell walls because of their needle shape [2]. Various studies have shown that single-walled nanotubes are potentially very good agents for the delivery of anticancer drugs [3], [4]. However, the toxicity of CNTs to tissues is still being studied [5]. Since the discovery of CNTs, many efforts have been made to discover non-CNTs due to the dependence of the properties of CNTs on the nanotube diameter and chiral features. Thereafter, boron nitride nanotubes (BNNTs) were first synthesized in 1995 [6]. These nanotubes, similar to their carbon counterparts, have excellent mechanical properties due to the strong sp3 bonds in the nanotube walls [7], [8].

BNNTs are characterized by remarkable mechanical and electrical properties, such as a wide band gap (3.5–5.5 eV) [9], good piezoelectric properties, high thermal and chemical stability [10], and high oxidation resistance [11], [12]. Their unique mechanical properties and high thermal conductivity [13] are invaluable for diagnostic and therapeutic approaches to diseases as well as sensor-based applications. BNNTs are hydrophobic and insoluble in water, and their resistance to oxidation makes them useful as drug carriers [14]. In addition, BNNTs are non-toxic to cells. They do not damage the DNA [15]. Ciofani et al. tested the non-toxicity of BNNTs [16], [17]. Their results showed that the chemical neutrality and structural stability of these nanotubes is attributable to their biocompatibility [18].

Following the discovery of BNNTs in 1994 by Rubio et al. [19] and their synthesis by Chopra et al. in 1995 [6], [20], Deca et al. studied the interactions between the (10, 0) and (10, 5) nanotubes with the drug molecule isoniazid (INH) [21]. They showed that the binding energy of INH to BNNT (5, 5) was slightly higher than that of BNNT (10, 0). Mukhopadhyay et al. studied the adsorption of tryptophan (a non-polar amino acid), sparic acid, and arginine (a polar amino acid) on BNNTs, and reported a strong bonding energy for the adsorption of the polar amino acid on the BNNT surface [22]. Peyghan et al. investigated the adsorption and electrical structure of the BNNT (6, 0) imidazole molecule in the gaseous and soluble phases. They found that imidazole adsorption had no significant effect on the electrical structure of the BNNT [23]. Yang et al. studied the interaction between BNNTs with biological molecules using density-functional theory (DFT) calculations [24]. Anota et al. investigated the interaction between BNNT and metformin using DFT [25]. Recently, the interaction between the uracil molecule and BNNT (n, 0) was investigated by Mirzai et al. [26]. Given the widespread use of BNNTs, many theoretical investigations have been conducted on the adsorption of different molecules onto the surface of various nanostructures, such as aluminum nitride and silicon carbide [27], [28], [29], [30], [31], [32], [33], [34].

Bromochlorodifluoromethane (BCF), also known as halon 1211, halon 1211 BCF, or freon 12B1, has many applications in industries as well as daily life. BCF is a proficient fire extinguishing agent and exhibits lower toxicity compared to carbon tetrachloride [35], [36]. The BCF is classified as a chlorofluorocarbon; therefore, its ozone depletion potential is high. Care should be taken when using this substance, and currently, the production of BCF is limited in most countries, but it continues to be recycled. Similar investigations have been performed to detect Ozone-depleting substances. For example Scaranto et al. theoretically studied the CH2BrF adsorption on TiO2 surface [37], Mohammadi et al. provided DFT modelling for adsorption of CH3Br using different nanotubes [28], Esrafili et al. performed a study on N2O [38], Gholizadeh et al investigated the adsorption of CO on Si-and Se-doped graphenes [39]. Other pollutants are also studied like Hydrochlorofluorocarbons [40], NO [41], CH2F2 [42], NO2 and NO3 [43]. Accordingly, it is important to study the feasibility of the adsorption of BCF by using the nano-material surface.

This article discusses the design of such a sensor. This study investigated the interactions of BCF with BNNT and BN nanotubes doped with Al, Ga, P, and As. The structure of BN was optimized using Gaussian software to study the chemical stability and conductivity characteristics, following which the element doping process was investigated. Different structures need to be optimized using appropriate computational methods. The computation method should be highly sensitive to precisely determine the energies of the molecular orbitals and allow an in-depth understanding of the conductivity and probability of physical and chemical adsorption. For this purpose, the Perdew, Burke, and Ernzerhof exchange–correlation (PBEPBE) as well as B3LYP-D3 functionals and 6-311G (d) basis set were used in this research for the computations. The B3LYP, CAM-B3LYP, ωB97XD, and M06-2X functionals with the 6-311G (d) basis set were also used to calculate the single-point energies. The natural bond orbital (NBO) and quantum theory of atoms in molecule (QTAIM) were implemented with the PBEPBE/6-311G (d) method, and the results were used to obtain various physical parameters.

Section snippets

Computational details

The periodic boundary condition DFT (PBC-DFT) calculations at both PBEPBE [44] and B3LYP-D3 [45], [46], [47] functionals together with the 6-311G (d) Pople split-valence triple zeta basis set with polarization functions [48] were used for geometry optimization of all different positions of the BCF/nanotube complex structures. All the calculations, including geometry optimization, single-point energy calculations, and NBO analysis, were performed with the Gaussian 16 package [49], [50]. It

Structural analysis

To optimize the structure of pristine armchair (5, 5) single-walled BNNTs using periodic boundary conditions, we first considered a base cell of B and N atoms (B20N20) whose length is 5.038 Å. Unlike the nanosheet, the nanotube was expanded in one direction only. We optimized this cell using the 1D periodic boundary condition DFT method with the PBEPBE functional together with the basis set 6-311G (d). A 5 × 1 × 1k-point sampling in the Brillion zone was employed in such a way that, by

Conclusion

In this study, the interactions between BCF molecules and pristine, Al-, Ga-, P-, and As-doped BNNTs were investigated using the density functional framework. The structures of the nanotubes and BCF molecule were optimized using the PBEPBE/6-311G (d) level of theory. The B3LYP, CAM-B3LYP, M06-2X, and ωB97XD functionals and the same basis set were also used to consider the contribution of long-range interactions and the dispersion effect. QTAIM and NBO analyses were implemented to consider the

CRediT authorship contribution statement

Mohsen Doust Mohammadi: Investigation, Writing - original draft. Hewa Y. Abdullah: Conceptualization, Writing - review & editing, Resources, Supervision.

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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