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Cyclosarin nerve agent interaction with the pristine, Stone Wales defected, and Si-doped BN nanosheets: Theoretical study
Physica E 90 (2017) 143–148
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Physica E journal homepage: www.elsevier.com/locate/physe
Cyclosarin nerve agent interaction with the pristine, Stone Wales defected, and Si-doped BN nanosheets: Theoretical study ⁎
MARK
⁎
K. Nejatia, S. Arshadia, E. Vessallya, , A. Bekhradniab, , A. Hosseinianc a b c
Department of Chemistry, Payame Noor University, Tehran, Iran Pharmaceutical Sciences Research Center, Department of Medicinal Chemistry, Mazandaran University of Medical Sciences, Sari, Iran Department of Engineering Science, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran, Iran
A R T I C L E I N F O
A BS T RAC T
Keywords: BN hexagonal sheet Cyclosarin White graphene DFT Sensor
Never agent identification and disposal is vital for both civilian and military defense resources. Herein, using density functional theory calculations, the reactivity and electronic sensitivity of pristine, Stone Wales (SW) defected, and Si-doped BN (Si-BN) nanosheets toward cyclosarin nerve agent were investigated. It was found that the interaction of cyclosarin with the pristine BN sheet is very weak and also that is not energetically favorable with SW defected one. Unlike the SW defect, replacing a B atom by Si atom significantly makes the cyclosarin adsorption energetically favorable. Calculations show that the carbonyl and etheric oxygen atoms of cyclosarin attack the Si atom of Si-BN with the adsorption energies of −73.5 and −136.9 kJ/mol, respectively. The cyclosarin nerve agent can be decomposed by the Si-BN sheet which is thermodynamically highly favorable. Upon this process, the HOMO and LUMO levels are significantly unstabilized and the HOMO-LUMO gap significantly changed by about 24.2%. The cyclosarin presence and its decomposition by Si-BN sheet can be recognized because of the electrical conductivity change of the sheet.
1. Introduction Decomposition of nerve agents is an important chemical process for hazardous chemical wastes disposal [1]. Also, their identification is vital for both civilian and military defense resources [2]. To date, many methods have been introduced for nerve agent detection and decomposition [3–5]. By advent of nanotechnology, nanostructures have attracted an extensive attention as gas sensors, and surfaces for gas adsorption and decomposition because of their surface/volume ratio [6–17]. Single-walled carbon nanotubes have been used to recognize nerve agents with reproducible resistance change [18]. However, practically, working with carbon nanotubes is a hard task due to their electronic dependency on the chirality [19]. Recently, a great attention has been devoted to the inorganic BN nanostructures whose electronic properties are less depended on the chirality which makes them more suitable for electronic devices [20–23]. An important isostructural arrangement of graphene is hexagonal BN nanosheet ‘white graphene’ which has been synthesized using various methods [24]. Many researchers investigated the gas adsorption and sensing properties of the withe graphene [25–29]. Also, doping, creating defects, and functionalization approaches have been investigated as strategies to tailor the reactivity and sensitivity of
⁎
nanomaterials [30–39]. It has been indicated that BN nanosheet can be employed in the pristine form for detection of NO2 gas and in the Aldoped form for sensing the nitrophenol [30]. Computational methods significantly help the experimentalist to understand the adsorption and sensing behavior of different surfaces to chemicals. In this letter, we explore the adsorption behavior and sensitivity the pristine, StoneWales detected (SW-BN) and Si-doped BN (Si-BN) nanosheets to cyclosarin nerve agent by means of density functional theory (DFT) calculations. Experimentally, several works have been published on the synthesis of different Si-BN nanomaterials [40–42]. Fan et al. have reported the growth of silicon-doped BN nanotubes via catalyst-assisted pyrolysis of a boron-containing polymeric precursor, characterizing their morphologies and structures using electron microscopy and Raman spectroscopy [40]. Also, Si-doped BN films with various Si concentrations were obtained by in situ cosputtering during ion beam assisted deposition by Ying et al. [41]. Si-doped multiwalled BN nanotubes were synthesized via thermal chemical vapor deposition by Cho et al. [42]. Electron energy-loss spectroscopy showed that 5% of Si atoms were homogeneously doped into the nanotubes. X-ray absorption and photoelectron spectroscopy measurements indicated that the Si−B and Si−N bonding structures are produced.
Corresponding authors. E-mail addresses: [email protected] (E. Vessally), [email protected] (A. Bekhradnia).
http://dx.doi.org/10.1016/j.physe.2017.03.023 Received 30 November 2016; Received in revised form 13 February 2017; Accepted 27 March 2017 Available online 27 March 2017 1386-9477/ © 2017 Elsevier B.V. All rights reserved.
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(~5.50 eV) [53]. To obtain the stable cyclosarin/BN complexes, several initial structures entailing single atom (F, O, and H), two, three, and more atoms near the surface of the BN were explored. It was predicted that the molecule tends to escape from the surface of BN sheet upon the relax optimization and a weak interaction is predicted. Finally, in the most stable form, the cyclosarin located on the surface of the BN as shown in Fig. 1 with adsorption energy of about −1.32 kJ/mol. Because of this weak interaction, the electronic properties of the BN sheet are not significantly affected by the adsorption process.
2. Computational methods The all calculations were performed using the B3LYP functional augmented with an empirical dispersion term (B3LYP-D) and the 6– 31G* basis set as implemented in the GAMESS code [43]. B3LYP delivers an efficient and robust basis for III–V semiconductor calculation and has been frequently used for nanomaterials [44–51]. We used a model of BN nanosheet which is consisted from 36 B and 36 N atoms that its dangling bonds is saturated with hydrogen atoms to reduce the boundary effects. Previously, this model has been frequently used for different purposes and it has been indicated that it is a good representative for larger BN nanosheets [25–27,29,30]. GaussSum code was hired to attain DOS results [52]. The adsorption energy (Ead) is predicted as follows:
3.2. The adsorption of cyclosarin on the SW-BN sheet The optimized structure of SW-BN sheet is shown in Fig. 2. As it was schematically indicated (Fig. 2), for creating SW defect, four adjacent hexagonal rings at the center of BN sheet are changed into two pentagonal and two heptagonal rings when the bond uniting two of the adjacent rings rotates. Length of the rotated bond is change from 1.44 to 1.39 Å due to a structural distortion. Upon the SW-defect formation an N-N and a B-B bond are formed with length of about 1.48 and 1.67 Å, respectively. The energy is needed for SW defect formation is calculated to be about −133.6 kcal/mol. In the other words, the pristine BN sheet is more stable than the SW-BN by about 133.6 kcal/ mol. The HOMO is unstabilized by about 0.48 eV by shifting from −6.30 eV in the pristine BN sheet to −5.82 eV in the SW-BN sheet. While the LUMO is stabilized by changing from −0.42 to −0.81 eV. Also, their shapes are significantly changed by localizing on the newly formed B-B (LUMO) and N-N (HOMO) bonds as shown in Fig. 2. Finally, the Eg is somewhat decreased from 5.88 to 5.01 eV, indicating that existence of SW defects decreases the electrical resistance of the BN sheet. As it was mentioned before the calculated Eg of the pristine BN is larger than that of the experimental value which may be due to the naturally existence of defects in the real BN sheet. It is expected that the high electron heads (O-head and F-head) of cyclosarin molecule attack the electron deficient B-B site of the SW defect. Our calculations indicate that when the molecule is located from its F head on the B-B site, it reoriented and tends to attach from its carbonyl O-head to a B atom of B-B bond as shown in Fig. 3. The length of newly formed O-B is about 1.75 Å and a local deformation is occurred in the adsorption site. The adsorbing B atom is projected out of plan and the lengths of its surrounding bonds are perturbed. These findings show that the interaction between the cyclosarin molecule and SW-BN sheet is much stronger than that with the pristine BN sheet. But the calculated adsorption energy is positive for this interaction (Table 1) because of the large structural deformation that compensates the released energy. To show the strength of the adsorption we used the following equation to find the binding energy:
Ead = E (cyclosarin/adsorbent) − E (adsorbent) − E (cyclosarin) + E (BSSE) (1) where E(adsorbent) is the total energy of a pristine, SW-BN or Si-BN sheet. E (cyclosarin/ adsorbent) is the total energy of the complex of the adsorbed cyclosarin molecule on the adsorbent. E (BSSE) is the basis set superposition error (BSSE) corrected for all adsorption energies. To predict the electronic sensitivity Eq. (2) was used which relates the HOMO-LUMO gap (Eg) to the electrical conductivity of a semiconductor as follows:
σ = A T3/2 exp (−Eg/2kT)
(2) 3
3/2
where k is the Boltzmann's constant and A (electrons/m K constant.
) is a
3. Results and discussion 3.1. The cyclosarin on the pristine BN sheet We have shown the structure of BN nanosheet in Fig. 1, revealing that the B-N bond lengths are about 1.44–1.47 Å in agreement with previous reports [25]. The HOMO and LUMO of the sheet are lied at −6.30 and −0.42 eV, respectively, representing an Eg of about 5.88 eV which is approximately in accordance with the experimental bad gap
Ebin = E (cyclosarin/SW−BN) − Esp (SW−BN) − Esp (cyclosarin) + E (BSSE)
(3)
where E (cyclosarin/SW-BN) is total energy of cyclosarin/SW-BN complex, and Esp (SW-BN) is single point energy of the SW-BN after removing the cyclosarin from the complex and also Esp (cyclosarin) is the single point energy of cyclosarin after removing the SW-BN from the complex. Finally the predicted binding energy is predicted to be about −63.2 kJ/mol, indicating a strong interaction. The HOMO and LUMO levels are unstabilized upon the cyclosarin adsorption process. But Table 1 shows that the Eg of the SW-BN is not sensibly affected. Thus, the electrical conductivity of the SW-BN will not vary meaningfully based on the Eq. (2). It can be decided that although the SW defect considerably increases the reactivity of the BN sheet, its effect on the electrical sensitivity is negligible. 3.3. The cyclosarin adsorption on the Si-BN sheet Fig. 1. Optimized structure of BN nanosheet and its complex with cyclosarin nerve agent.
Herein, we will explore the effect of Si-doping on the reaction of the 144
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Fig. 2. (a) A schematic view for Stone Wales (SW) defect creation, (b) the SW defected BN nanosheet, and its (c) LUMO and, (d) HOMO levels. Distances in Å. Table 1 The adsorption energy (Ead, kJ/mol) for adsorption of cyclosarin on the pristine, Stone Wales (SW) defected, and Si-doped BN nanosheets. The energies of HOMO, LUMO, and HOMO-LUMO gap (Eg) are in eV. The %ΔEg indicates the change of Eg after the adsorption process. Structure
Ead
EHOMO
ELUMO
Eg
%ΔEg
BN BN/Sarin SW-BN SW-BN/Sarin Si-BN Complex A Complex B
– −1.32 – 37.6 – −73.5 −136.6
−6.30 −6.34 −5.82 −5.27 −4.84 −4.91 −4.11
−0.42 −0.39 −0.81 −0.25 −1.95 −1.72 −0.52
5.88 5.96 5.01 5.02 2.89 3.19 3.59
– 1.3 – 0.1 – 10.3 24.2
atom (~1.17 Å) than the N one (~0.75 Å) [56]. The optimized structure of the BN in which a B atom is replaced by Si atom (Si–BN sheet) is shown in Fig. 4. The geometry of BN sheet is noticeably distorted around the Si-doped site and the dopant Si atom projects out of the sheet surface to decrease the compressive stress. The length of newly formed Si-N bond is approximately 1.74 Å, and the Si NBO (natural bond orbitals) hybridization is almost sp3. The HOMO level of Si-BN sheet is singly occupied molecular orbital which significantly tends to accept electron to be fulfilled. As shown in Fig. 4, this level is largely localized on the dopant Si atom which makes it suitable for a nucleophilic attack. The energy of HOMO level of Si-BN sheet is higher than that of the pristine BN sheet by about 1.46 eV (Table 1) which makes its more accessible for the nucleophilic attack. The DOS plot (Fig. 4) indicates that two new states are appeared within the Eg of the BN sheet at −4.84 and −1.95 eV after the Si-doping process. The LUMO level of BN sheet is shifted from −0.42 to −1.95 eV and the Eg is narrowed by about 2.99 eV. It is well kwon that the smaller Eg causes lower kinetic stability and thereby more reactivity. Our calculations indicate that the cyclosarin molecule energetically
Fig. 3. The complex between Stone Wales defected BN sheet and cyclosarin molecule. Distance in Å.
cyclosarin with the BN sheet and also its effect on the electronic properties. Our desired purpose is increasing the sensitivity and reactivity of this sheet toward the nerve agent. Several Si-doped nanostructures have been previously inspected theoretically and also their synthesis has been reported [54,55]. It can be seen that a B or N atom can be replaced by Si atom. It has been previously shown [56] that replacing N atom by Si atom is energetically unfavorable and the structure of doped sheet is a saddle point with large imaginary frequencies. The imaginary frequency orientation has indicated that the dopant Si tends to escape from the sheet surface in this complex. This is due to very larger size of the Si atom compared to the N atom. However, the radius of Si atom (~1.46 Å) is more close to that of the B
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tends to attach to the Si atom via its carbonyl or etheric oxygen atom. When cyclosarin is located from its F atom on the Si atom, it reoriented and attached from oxygen atom to the Si dopant. When it is adsorbed from carbonyl oxygen, the complex A (Fig. 5) is obtained in which the newly formed O-Si bond is about 1.65 Å and an energy of about 73.5 kJ/mol is released. It should be noted that this large energy and structural deformation indicate that the recovery of the Si-BN will be a hard task. However, the main potential application of this compound may be decomposition and removal of the nerve agent in the state of emergency and war. Although at this condition the recovery of Si-BN may not be a vital concern, this may be a disadvantage of this compound. We used the Synchronous Transit-Guided Quasi-Newton (STQN) method [57] to predict the transition state (TS) structure for the adsorption process on the Si-BN. The predicted TS structure is shown in Fig. 1S (Supplementary material), indicating that the formed Si-O bond is about 1.89 Å which is shorter about 0.22 Å form that in the final structure. Also, the O-C bond is weakened and increased to 2.32 Å which is smaller than that in the final structure. The calculated energy barrier is about 61.2 kJ/mol which is not too large to be overcome at room temperature. The HOMO and LUMO are slightly changed and the Eg is changed by about 10.3% (Table 1). When the molecule attaches from its etheric oxygen atom, the cyclohexane ring is separated and an intermediate complex (B, Fig. 5) is created which tends to transform to the complex A. The adsorption energy about −136.6 kJ/mol indicates that the interaction is energetically highly favorable. This decomposition process is useful for disposal and removing the toxicity of this nerve agent which can be recognized because of a large change in the electronic properties of the Si-BN sheet. Upon the decomposition process, the HOMO and LUMO levels are significantly unstabilized. The HOMO is shifted from −4.84 to −4.11 eV and the LUMO from −1.95 to −0.52 eV. In accordance with the energy change, the shapes of the HOMO and LUMO are meaningfully changed. As shown in Fig. 6, the HOMO level of complex B is shifted on the hexagonal ring of the cyclosarin molecule and the LUMO is mainly focused on the edge of the sheet which is ended by the electron deficient B atoms. The change of the energy of the LUMO level is much more than that of the HOMO level, and thus, the Eg is significantly changed by about 24.2%. Based on the Eq. (2), this large change of the Eg will exponentially alter the electrical conductivity of the Si-BN sheet which can be converted to an electrical signal. Therefore, by appearing this signal the existence and decomposition of the cyclosarin can be recognized.
Fig. 4. Optimized structure of Si-doped BN sheet and its DOS plot and HOMO level profile. Distance in Å.
4. Conclusions We have studied the interaction between the cyclosarin nerve agent and pristine BN, SW-BN, and Si-BN nanosheets by means of DFT calculation. It was found that the interaction of this gas with the pristine BN sheet is very weak with adsorption energy of about −1.32 kJ/mol, and the electronic properties of the sheet are not affected sensibly. Creating a SW defect, significantly improves the interaction, but it is thermodynamically is unfavorable due to a large structural deformation. When a B atom is replaced by an Si one, the reactivity and electronic sensitivity of the sheet are considerably increased toward cyclosarin agent. It was revealed that cyclosarin is decomposed by the Si-BN, releasing an energy of 136.6 kJ/mol. The decomposition process significantly changes the Eg of the sheet by about 24.2%. This large change exponentially alters the electrical conductivity of the Si-BN sheet which can be converted to an electrical signal which identifies the existence and decomposition of the cyclosarin. Acknowledgements The authors gratefully acknowledge the financial support of this work by the Mazandaran University of Medical Sciences "Professor's Projects Funds".
Fig. 5. Optimized structure of cyclosarin/Si-doped BN sheet complexes. Distances in Å.
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Fig. 6. The HOMO and LUMO profiles of the complex B (Fig. 5).
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Appendix A. Supplementary material
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Supplementary data associated with this article can be found in the online version at doi:10.1016/j.physe.2017.03.023.
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Contents lists available at ScienceDirect
Physica E journal homepage: www.elsevier.com/locate/physe
Cyclosarin nerve agent interaction with the pristine, Stone Wales defected, and Si-doped BN nanosheets: Theoretical study ⁎
MARK
⁎
K. Nejatia, S. Arshadia, E. Vessallya, , A. Bekhradniab, , A. Hosseinianc a b c
Department of Chemistry, Payame Noor University, Tehran, Iran Pharmaceutical Sciences Research Center, Department of Medicinal Chemistry, Mazandaran University of Medical Sciences, Sari, Iran Department of Engineering Science, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran, Iran
A R T I C L E I N F O
A BS T RAC T
Keywords: BN hexagonal sheet Cyclosarin White graphene DFT Sensor
Never agent identification and disposal is vital for both civilian and military defense resources. Herein, using density functional theory calculations, the reactivity and electronic sensitivity of pristine, Stone Wales (SW) defected, and Si-doped BN (Si-BN) nanosheets toward cyclosarin nerve agent were investigated. It was found that the interaction of cyclosarin with the pristine BN sheet is very weak and also that is not energetically favorable with SW defected one. Unlike the SW defect, replacing a B atom by Si atom significantly makes the cyclosarin adsorption energetically favorable. Calculations show that the carbonyl and etheric oxygen atoms of cyclosarin attack the Si atom of Si-BN with the adsorption energies of −73.5 and −136.9 kJ/mol, respectively. The cyclosarin nerve agent can be decomposed by the Si-BN sheet which is thermodynamically highly favorable. Upon this process, the HOMO and LUMO levels are significantly unstabilized and the HOMO-LUMO gap significantly changed by about 24.2%. The cyclosarin presence and its decomposition by Si-BN sheet can be recognized because of the electrical conductivity change of the sheet.
1. Introduction Decomposition of nerve agents is an important chemical process for hazardous chemical wastes disposal [1]. Also, their identification is vital for both civilian and military defense resources [2]. To date, many methods have been introduced for nerve agent detection and decomposition [3–5]. By advent of nanotechnology, nanostructures have attracted an extensive attention as gas sensors, and surfaces for gas adsorption and decomposition because of their surface/volume ratio [6–17]. Single-walled carbon nanotubes have been used to recognize nerve agents with reproducible resistance change [18]. However, practically, working with carbon nanotubes is a hard task due to their electronic dependency on the chirality [19]. Recently, a great attention has been devoted to the inorganic BN nanostructures whose electronic properties are less depended on the chirality which makes them more suitable for electronic devices [20–23]. An important isostructural arrangement of graphene is hexagonal BN nanosheet ‘white graphene’ which has been synthesized using various methods [24]. Many researchers investigated the gas adsorption and sensing properties of the withe graphene [25–29]. Also, doping, creating defects, and functionalization approaches have been investigated as strategies to tailor the reactivity and sensitivity of
⁎
nanomaterials [30–39]. It has been indicated that BN nanosheet can be employed in the pristine form for detection of NO2 gas and in the Aldoped form for sensing the nitrophenol [30]. Computational methods significantly help the experimentalist to understand the adsorption and sensing behavior of different surfaces to chemicals. In this letter, we explore the adsorption behavior and sensitivity the pristine, StoneWales detected (SW-BN) and Si-doped BN (Si-BN) nanosheets to cyclosarin nerve agent by means of density functional theory (DFT) calculations. Experimentally, several works have been published on the synthesis of different Si-BN nanomaterials [40–42]. Fan et al. have reported the growth of silicon-doped BN nanotubes via catalyst-assisted pyrolysis of a boron-containing polymeric precursor, characterizing their morphologies and structures using electron microscopy and Raman spectroscopy [40]. Also, Si-doped BN films with various Si concentrations were obtained by in situ cosputtering during ion beam assisted deposition by Ying et al. [41]. Si-doped multiwalled BN nanotubes were synthesized via thermal chemical vapor deposition by Cho et al. [42]. Electron energy-loss spectroscopy showed that 5% of Si atoms were homogeneously doped into the nanotubes. X-ray absorption and photoelectron spectroscopy measurements indicated that the Si−B and Si−N bonding structures are produced.
Corresponding authors. E-mail addresses: [email protected] (E. Vessally), [email protected] (A. Bekhradnia).
http://dx.doi.org/10.1016/j.physe.2017.03.023 Received 30 November 2016; Received in revised form 13 February 2017; Accepted 27 March 2017 Available online 27 March 2017 1386-9477/ © 2017 Elsevier B.V. All rights reserved.
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(~5.50 eV) [53]. To obtain the stable cyclosarin/BN complexes, several initial structures entailing single atom (F, O, and H), two, three, and more atoms near the surface of the BN were explored. It was predicted that the molecule tends to escape from the surface of BN sheet upon the relax optimization and a weak interaction is predicted. Finally, in the most stable form, the cyclosarin located on the surface of the BN as shown in Fig. 1 with adsorption energy of about −1.32 kJ/mol. Because of this weak interaction, the electronic properties of the BN sheet are not significantly affected by the adsorption process.
2. Computational methods The all calculations were performed using the B3LYP functional augmented with an empirical dispersion term (B3LYP-D) and the 6– 31G* basis set as implemented in the GAMESS code [43]. B3LYP delivers an efficient and robust basis for III–V semiconductor calculation and has been frequently used for nanomaterials [44–51]. We used a model of BN nanosheet which is consisted from 36 B and 36 N atoms that its dangling bonds is saturated with hydrogen atoms to reduce the boundary effects. Previously, this model has been frequently used for different purposes and it has been indicated that it is a good representative for larger BN nanosheets [25–27,29,30]. GaussSum code was hired to attain DOS results [52]. The adsorption energy (Ead) is predicted as follows:
3.2. The adsorption of cyclosarin on the SW-BN sheet The optimized structure of SW-BN sheet is shown in Fig. 2. As it was schematically indicated (Fig. 2), for creating SW defect, four adjacent hexagonal rings at the center of BN sheet are changed into two pentagonal and two heptagonal rings when the bond uniting two of the adjacent rings rotates. Length of the rotated bond is change from 1.44 to 1.39 Å due to a structural distortion. Upon the SW-defect formation an N-N and a B-B bond are formed with length of about 1.48 and 1.67 Å, respectively. The energy is needed for SW defect formation is calculated to be about −133.6 kcal/mol. In the other words, the pristine BN sheet is more stable than the SW-BN by about 133.6 kcal/ mol. The HOMO is unstabilized by about 0.48 eV by shifting from −6.30 eV in the pristine BN sheet to −5.82 eV in the SW-BN sheet. While the LUMO is stabilized by changing from −0.42 to −0.81 eV. Also, their shapes are significantly changed by localizing on the newly formed B-B (LUMO) and N-N (HOMO) bonds as shown in Fig. 2. Finally, the Eg is somewhat decreased from 5.88 to 5.01 eV, indicating that existence of SW defects decreases the electrical resistance of the BN sheet. As it was mentioned before the calculated Eg of the pristine BN is larger than that of the experimental value which may be due to the naturally existence of defects in the real BN sheet. It is expected that the high electron heads (O-head and F-head) of cyclosarin molecule attack the electron deficient B-B site of the SW defect. Our calculations indicate that when the molecule is located from its F head on the B-B site, it reoriented and tends to attach from its carbonyl O-head to a B atom of B-B bond as shown in Fig. 3. The length of newly formed O-B is about 1.75 Å and a local deformation is occurred in the adsorption site. The adsorbing B atom is projected out of plan and the lengths of its surrounding bonds are perturbed. These findings show that the interaction between the cyclosarin molecule and SW-BN sheet is much stronger than that with the pristine BN sheet. But the calculated adsorption energy is positive for this interaction (Table 1) because of the large structural deformation that compensates the released energy. To show the strength of the adsorption we used the following equation to find the binding energy:
Ead = E (cyclosarin/adsorbent) − E (adsorbent) − E (cyclosarin) + E (BSSE) (1) where E(adsorbent) is the total energy of a pristine, SW-BN or Si-BN sheet. E (cyclosarin/ adsorbent) is the total energy of the complex of the adsorbed cyclosarin molecule on the adsorbent. E (BSSE) is the basis set superposition error (BSSE) corrected for all adsorption energies. To predict the electronic sensitivity Eq. (2) was used which relates the HOMO-LUMO gap (Eg) to the electrical conductivity of a semiconductor as follows:
σ = A T3/2 exp (−Eg/2kT)
(2) 3
3/2
where k is the Boltzmann's constant and A (electrons/m K constant.
) is a
3. Results and discussion 3.1. The cyclosarin on the pristine BN sheet We have shown the structure of BN nanosheet in Fig. 1, revealing that the B-N bond lengths are about 1.44–1.47 Å in agreement with previous reports [25]. The HOMO and LUMO of the sheet are lied at −6.30 and −0.42 eV, respectively, representing an Eg of about 5.88 eV which is approximately in accordance with the experimental bad gap
Ebin = E (cyclosarin/SW−BN) − Esp (SW−BN) − Esp (cyclosarin) + E (BSSE)
(3)
where E (cyclosarin/SW-BN) is total energy of cyclosarin/SW-BN complex, and Esp (SW-BN) is single point energy of the SW-BN after removing the cyclosarin from the complex and also Esp (cyclosarin) is the single point energy of cyclosarin after removing the SW-BN from the complex. Finally the predicted binding energy is predicted to be about −63.2 kJ/mol, indicating a strong interaction. The HOMO and LUMO levels are unstabilized upon the cyclosarin adsorption process. But Table 1 shows that the Eg of the SW-BN is not sensibly affected. Thus, the electrical conductivity of the SW-BN will not vary meaningfully based on the Eq. (2). It can be decided that although the SW defect considerably increases the reactivity of the BN sheet, its effect on the electrical sensitivity is negligible. 3.3. The cyclosarin adsorption on the Si-BN sheet Fig. 1. Optimized structure of BN nanosheet and its complex with cyclosarin nerve agent.
Herein, we will explore the effect of Si-doping on the reaction of the 144
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Fig. 2. (a) A schematic view for Stone Wales (SW) defect creation, (b) the SW defected BN nanosheet, and its (c) LUMO and, (d) HOMO levels. Distances in Å. Table 1 The adsorption energy (Ead, kJ/mol) for adsorption of cyclosarin on the pristine, Stone Wales (SW) defected, and Si-doped BN nanosheets. The energies of HOMO, LUMO, and HOMO-LUMO gap (Eg) are in eV. The %ΔEg indicates the change of Eg after the adsorption process. Structure
Ead
EHOMO
ELUMO
Eg
%ΔEg
BN BN/Sarin SW-BN SW-BN/Sarin Si-BN Complex A Complex B
– −1.32 – 37.6 – −73.5 −136.6
−6.30 −6.34 −5.82 −5.27 −4.84 −4.91 −4.11
−0.42 −0.39 −0.81 −0.25 −1.95 −1.72 −0.52
5.88 5.96 5.01 5.02 2.89 3.19 3.59
– 1.3 – 0.1 – 10.3 24.2
atom (~1.17 Å) than the N one (~0.75 Å) [56]. The optimized structure of the BN in which a B atom is replaced by Si atom (Si–BN sheet) is shown in Fig. 4. The geometry of BN sheet is noticeably distorted around the Si-doped site and the dopant Si atom projects out of the sheet surface to decrease the compressive stress. The length of newly formed Si-N bond is approximately 1.74 Å, and the Si NBO (natural bond orbitals) hybridization is almost sp3. The HOMO level of Si-BN sheet is singly occupied molecular orbital which significantly tends to accept electron to be fulfilled. As shown in Fig. 4, this level is largely localized on the dopant Si atom which makes it suitable for a nucleophilic attack. The energy of HOMO level of Si-BN sheet is higher than that of the pristine BN sheet by about 1.46 eV (Table 1) which makes its more accessible for the nucleophilic attack. The DOS plot (Fig. 4) indicates that two new states are appeared within the Eg of the BN sheet at −4.84 and −1.95 eV after the Si-doping process. The LUMO level of BN sheet is shifted from −0.42 to −1.95 eV and the Eg is narrowed by about 2.99 eV. It is well kwon that the smaller Eg causes lower kinetic stability and thereby more reactivity. Our calculations indicate that the cyclosarin molecule energetically
Fig. 3. The complex between Stone Wales defected BN sheet and cyclosarin molecule. Distance in Å.
cyclosarin with the BN sheet and also its effect on the electronic properties. Our desired purpose is increasing the sensitivity and reactivity of this sheet toward the nerve agent. Several Si-doped nanostructures have been previously inspected theoretically and also their synthesis has been reported [54,55]. It can be seen that a B or N atom can be replaced by Si atom. It has been previously shown [56] that replacing N atom by Si atom is energetically unfavorable and the structure of doped sheet is a saddle point with large imaginary frequencies. The imaginary frequency orientation has indicated that the dopant Si tends to escape from the sheet surface in this complex. This is due to very larger size of the Si atom compared to the N atom. However, the radius of Si atom (~1.46 Å) is more close to that of the B
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tends to attach to the Si atom via its carbonyl or etheric oxygen atom. When cyclosarin is located from its F atom on the Si atom, it reoriented and attached from oxygen atom to the Si dopant. When it is adsorbed from carbonyl oxygen, the complex A (Fig. 5) is obtained in which the newly formed O-Si bond is about 1.65 Å and an energy of about 73.5 kJ/mol is released. It should be noted that this large energy and structural deformation indicate that the recovery of the Si-BN will be a hard task. However, the main potential application of this compound may be decomposition and removal of the nerve agent in the state of emergency and war. Although at this condition the recovery of Si-BN may not be a vital concern, this may be a disadvantage of this compound. We used the Synchronous Transit-Guided Quasi-Newton (STQN) method [57] to predict the transition state (TS) structure for the adsorption process on the Si-BN. The predicted TS structure is shown in Fig. 1S (Supplementary material), indicating that the formed Si-O bond is about 1.89 Å which is shorter about 0.22 Å form that in the final structure. Also, the O-C bond is weakened and increased to 2.32 Å which is smaller than that in the final structure. The calculated energy barrier is about 61.2 kJ/mol which is not too large to be overcome at room temperature. The HOMO and LUMO are slightly changed and the Eg is changed by about 10.3% (Table 1). When the molecule attaches from its etheric oxygen atom, the cyclohexane ring is separated and an intermediate complex (B, Fig. 5) is created which tends to transform to the complex A. The adsorption energy about −136.6 kJ/mol indicates that the interaction is energetically highly favorable. This decomposition process is useful for disposal and removing the toxicity of this nerve agent which can be recognized because of a large change in the electronic properties of the Si-BN sheet. Upon the decomposition process, the HOMO and LUMO levels are significantly unstabilized. The HOMO is shifted from −4.84 to −4.11 eV and the LUMO from −1.95 to −0.52 eV. In accordance with the energy change, the shapes of the HOMO and LUMO are meaningfully changed. As shown in Fig. 6, the HOMO level of complex B is shifted on the hexagonal ring of the cyclosarin molecule and the LUMO is mainly focused on the edge of the sheet which is ended by the electron deficient B atoms. The change of the energy of the LUMO level is much more than that of the HOMO level, and thus, the Eg is significantly changed by about 24.2%. Based on the Eq. (2), this large change of the Eg will exponentially alter the electrical conductivity of the Si-BN sheet which can be converted to an electrical signal. Therefore, by appearing this signal the existence and decomposition of the cyclosarin can be recognized.
Fig. 4. Optimized structure of Si-doped BN sheet and its DOS plot and HOMO level profile. Distance in Å.
4. Conclusions We have studied the interaction between the cyclosarin nerve agent and pristine BN, SW-BN, and Si-BN nanosheets by means of DFT calculation. It was found that the interaction of this gas with the pristine BN sheet is very weak with adsorption energy of about −1.32 kJ/mol, and the electronic properties of the sheet are not affected sensibly. Creating a SW defect, significantly improves the interaction, but it is thermodynamically is unfavorable due to a large structural deformation. When a B atom is replaced by an Si one, the reactivity and electronic sensitivity of the sheet are considerably increased toward cyclosarin agent. It was revealed that cyclosarin is decomposed by the Si-BN, releasing an energy of 136.6 kJ/mol. The decomposition process significantly changes the Eg of the sheet by about 24.2%. This large change exponentially alters the electrical conductivity of the Si-BN sheet which can be converted to an electrical signal which identifies the existence and decomposition of the cyclosarin. Acknowledgements The authors gratefully acknowledge the financial support of this work by the Mazandaran University of Medical Sciences "Professor's Projects Funds".
Fig. 5. Optimized structure of cyclosarin/Si-doped BN sheet complexes. Distances in Å.
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Appendix A. Supplementary material
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Supplementary data associated with this article can be found in the online version at doi:10.1016/j.physe.2017.03.023.
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