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First principles investigations of Cobalt and Manganese doped Boron Nitride Nanosheet for Gas Sensing Application

March 2023
Applied Surface Science 623:157083

March 2023
623:157083

DOI:10.1016/j.apsusc.2023.157083

Authors:

Mohammad Tanvir Ahmed

Jashore University of Science and Technology

Sayedul Hasan

Jahangirnagar University

Shariful Islam

Jahangirnagar University

Farid Ahmed

Jahangirnagar University

In the present study, Cobalt (Co) and Manganese (Mn) doped Boron Nitride nanosheet (BNNS) has been designed for density functional theory calculation. The variation in structural, electronic, and optical properties of BNNS due to Co and Mn doping has been studied along with the gas sensing ability of the designed nanosheets towards CH4, H2S, NH3, O3, PH3, and SO2 hazardous gases. Co and Mn doping in the BNNS result in an insulator-to-conductor and insulator-to-semiconductor transition, respectively. Co and Mn-doped BNNS show a stronger interaction with the selected gases resulting in high adsorption energy. The designed sheets show the strongest interaction with the O3 molecule resulting in a very high recovery time. Though doping results in significant structural deformation of the BNNS, a slight variation in bond length is observed due to gas adsorption. BNNS demonstrate a substantial drop in the band gap due to O3 and SO2 adsorption. In other cases, significant variations in the band gap of all the designed sheets are observed after gas adsorption. All the structures show a very high absorption coefficient of 105 cm-1 order which shows a slight peak shifting due to the interaction with toxic gases.

The geometry of pristine and gas-adsorbed BNNS

…

Band structures of pristine and gas-adsorbed BNNS

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Band structures of pristine and gas-adsorbed Co-BNNS

…

Real part of complex dielectric function for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

…

Refractive index for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

…

Figures - uploaded by Mohammad Tanvir Ahmed

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Content uploaded by Mohammad Tanvir Ahmed

Content may be subject to copyright.

First principles investigations of Cobalt and Manganese doped Boron

Nitride Nanosheet for Gas Sensing Application

Mohammad Tanvir Ahmed1, Sayedul Hasan2, Shariful Islam2, a, and Farid Ahmed2

1 Department of Physics, Jashore University of Science and Technology, Jashore, Bangladesh

2 Department of Physics, Jahangirnagar University, Dhaka 1342, Bangladesh

a Corresponding Author's Email: s_islam@juniv.edu

Abstract

In the present study, Cobalt (Co) and Manganese (Mn) doped Boron Nitride nanosheet (BNNS) has

been designed for density functional theory calculation. The variation in structural, electronic, and

optical properties of BNNS due to Co and Mn doping has been studied along with the gas sensing ability

of the designed nanosheets towards CH4, H2S, NH3, O3, PH3, and SO2 hazardous gases. Co and Mn

doping in the BNNS result in an insulator-to-conductor and insulator-to-semiconductor transition,

respectively. Co and Mn-doped BNNS show a stronger interaction with the selected gases resulting in

high adsorption energy. The designed sheets show the strongest interaction with the O3 molecule

resulting in a very high recovery time. Though doping results in significant structural deformation of

the BNNS, a slight variation in bond length is observed due to gas adsorption. BNNS demonstrate a

substantial drop in the band gap due to O3 and SO2 adsorption. In other cases, significant variations in

the band gap of all the designed sheets are observed after gas adsorption. All the structures show a very

high absorption coefficient of 105 cm-1 order which shows a slight peak shifting due to the interaction

with toxic gases.

Keywords: DFT; boron nitride; gas sensor; recovery time; adsorption.

Introduction

Rapid industrialization has increased environmental pollution from industrial wastes and other

byproducts, which requires continuous monitoring. The environment contains a variety of hazardous

gases, such as CH4, CO, SO2, CO2, NO, NH3, CH3OH, H2S, O3, PH3, and COCl2, which are produced

by motorized traffic, power plants, industry, biological waste, and other factors [1–7]. Although CH4 is

not a hazardous gas, it is highly flammable and can be poisonous to the lungs if inhaled in large amounts

[3]. The H2S is an acidic, flammable, and toxic gas that can harm the nervous system severely and

permanently [5]. PH3 is a highly toxic gas that can damage the kidney, nervous, and respiratory systems

due to excessive exposure [6]. Ozone exposure harms the lungs and extrapulmonary organs when

inhaled for a long time [7]. At concentrations over a certain threshold, SO2 may seriously injure humans

and the environment [5].

In order to provide a better living environment, monitoring these hazardous gases is essential, which is

what motivated the development of novel methods of sensing these gases [8]. Researchers have gained

a keen interest in two-dimensional (2D) materials due to the historic discovery of graphene. However,

graphene is unsuitable for sensing applications due to zero band gap and poor sensitivity [9].

Researchers have identified graphene-like hexagonal boron nitride (BN) as a promising gas-sensing

material. BN possesses better structural, chemical, and thermal stability, enhanced optical properties,

and a wide band gap compared to graphene [10–12]. BN is a potential gas-detecting material, especially

for severe environments, due to its strong thermal conductivity and excellent thermal stability. Various

gas molecules (NO2, NO, NH3, CO, CH4, H2, etc.) have been adsorbing to the surface of BN both

computationally and experimentally [13–16]. Boron nitride nanosheets (BNNS) produced

experimentally showed great sensitivity to methane gas [17]. Khan et al. studied the borophene/BN

interface, which strongly interacted with various industrial gases [18]. Mawwa et al. studied SO2 and

CO adsorption on in-plane graphene/BNNS, which showed better interaction with SO2 than CO [19].

Young et al. reported that carbon nitride (CN) monolayer showed a high sensitivity for H2S, NO, and

NH3 at room temperature [20]. According to the investigation of Mohammadi and Hamzehloo, BN

nanotubes and Carbon nanotubes showed physisorption, whereas Aluminum nitride nanotubes and

silicon carbide nanotubes showed strong chemisorption of CH3Br [21]. Bian et al. synthesized porous

BN, which showed a fast response toward H2S gas [22].

Doping of elements on BN structure is one of the ways to improve the gas sensing performance. Sazzad

et at. fabricated Carbon doped BNNS, which showed a strong sensing ability for methane gas [16].

According to the study of Fadlallah et al., Al-doped BN nanocones show higher sensitivity for NO2 and

SO2 compared to intrinsic BN nanocones [23]. Al and Ga-doped BN nanotube showed strong interaction

with NH3 gas, whereas Al and Ga-doped BNNS showed high sensitivity toward halomethanes [24,25].

Pi et al. studied the DFT analysis of Ni-doped BN nanotube, which showed strong adsorption of SO2

gas [26]. Yadav et al. studied the doping effect of Cr, Ni, Si, O, Al, C, and S on BNNS, where C-doped

BNNS proved to be a potential material for NO2 adsorption [27]. Al and Si-doped BN nanostructure

was designed by Moladoust et al., which showed higher adsorption energy for phosgene gas compared

to pristine BN structure [28]. Mn-doped BN nanotube showed promising sensing ability toward SO2

gas [29]. Cobalt (Co)-transition metal co-doped BNNS reported as promising materials for spintronic

applications [10]. Co-doped BN nanotube showed strong interaction with CO2 gas [30]. BNNS showed

strong binding energy with different metallic dopants, e.g., Co, Mn, Fe, Ni, and so on [31]. Tizroespeli

et al. investigated the magnetic, optical, and electronic properties of Cobalt (Co) and Manganese (Mn)

doped BNNS, which showed outstanding potential for spintronic and optoelectronic performance [32].

The remarkable properties of Co and Mn-doped BNNS and BN nanotube inspired us to study further

the gas sensing ability of Co and Mn-doped BNNS.

Here we studied the effect of Cobalt (Co) and Manganese (Mn) doping on the BNNS and observed the

variations in structural, electronic, and optical properties due to doping. We also studied and compared

the sensing ability of BNNS, Co-doped BNNS (Co-BNNS), and Mn-doped BNNS (Mn-BNNS) towards

CH4, H2S, NH3, O3, PH3, and SO2 hazardous gas molecules. To our best knowledge, similar studies on

the Co, Mn-doped BNNS have not been reported before.

Computational Details

All the simulations were performed using the plane-wave ultrasoft pseudopotential based on the density

functional theory (DFT) throughout the Cambridge Serial Total Energy Package (CASTEP) [33]. The

contribution to optoelectronic properties was investigated by taking into account the valance electrons

of Nitrogen (N), Boron (B), Cobalt (Co), and Manganese (Mn). For the exchange-correlation correction,

the generalized gradient approximation of the Perdew-Burke-Ernzerhof method was utilized [34].

Broyden–Fletcher–Goldfarb–Shanno (BFGS) minimization algorithm was employed for structural

optimization [35]. For better optoelectronic properties, we construct 4×4×1 supercells of hexagonal BN

nanosheet structure where a 3×3×1 k-point mesh following the scheme of Monkhorst-Pack was used to

calculate the electronic and optical properties [33]. The effect of different plane-wave cutoff (PWC)

energies, i.e., 330 eV, 350 eV, 370 eV, and 400 eV, was studied in the optimization process of the

pristine BNNS structure among which the minimum energy was obtained via 400 eV PWC energy.

Hence, plane-wave cutoff energy of 400 eV was used throughout the rest of the computations. Geometry

optimization was accomplished by using convergence criteria of maximum stress to be 0.05 GPa, 3×10-

2 eV/atom for maximum force, 1.0×10-5 eV/atom for total energy, and 0.001 Å for displacement [33].

While doping, one B atom was replaced by Co or Mn atom. In order to study the sensitivity of the

nanosheets toward the toxic gas molecules, the adsorption energy (Eads) was calculated by the following

equation.

      .

(1)

Where, ENS+gas, ENS, and Egas represent the energy of the gas-adsorbed nanosheet, nanosheet (without

gas molecule), and gas molecule, respectively. The stability of the adsorbed gas on the nanosheets is

verified by the negative adsorption energy and the real phonon frequency [29]. The phonon frequency

was not studied in this research for simplicity; however, the stable adsorption configuration was

obtained using the adsorption locator module [36–38].

Results and Discussion

Geometric Analysis

Table 1: Bond Length (Å) variation due to gas adsorption on BNNS

Bond

type

BNNS

BNNS+CH4

BNNS+H2S

BNNS+NH3

BNNS+O3

BNNS+PH3

BNNS+SO2

B-N

1.449

C-H

1.095

(1.096)

S-H

1.35

(1.358)

N-H

1.0296

(1.024)

O-O

1.293

(1.280)

O=O

1.289

(1.277)

P-H

1.425

(1.429)

S=O

1.45

(1.451)

The studied geometrical bond lengths between different atoms (i.e., boron, Carbon, nitrogen, hydrogen,

oxygen, phosphorus, and sulfur) of the optimized structure of BNNS (before and after the adsorption

of different gas molecules) are represented in Figure 1. The values in the parenthesis represent the

atomic bond length of the gas molecules before adsorption (Table 1). According to the study, the

average B-N bond lengths do not seem to vary due to adsorption, which signifies a negligible

deformation of the BNNS after interaction with gases. The bond lengths of the BNNS satisfy previous

reports [39]. However, a significant change in the bond lengths of the gas molecules is observed after

adsorption. The average B-N bond lengths have slightly varied due to Co (Table 2) and Mn (Table 3)

doping. The Co-N and Mn-N bond lengths satisfy previous reports [40–42]. For both Co and Mn-doped

BNNS, slight structural deformation is observed due to adsorption. Figure 2 and Figure 3 show the

geometry of pristine and gas-adsorbed Co-BNNS and Mn-BNNS, respectively.

Figure 1: The geometry of pristine and gas-adsorbed BNNS

Figure 2:The geometry of pristine and gas-adsorbed Co-BNNS

Figure 3:The geometry of pristine and gas-adsorbed Mn-BNNS

Table 2:Bond Length (Å) variation due to gas adsorption on Co-BNNS

Bond type

Co-

BNNS

Co-BNNS

+ CH4

Co-BNNS

+ H2S

Co-BNNS

+ NH3

Co-BNNS

+ O3

Co-BNNS

+ PH3

Co-BNNS

+ SO2

B-N

1.452

1.453

1.45

1.452

1.45

Co-N

1.81

1.815

1.837

1.847

1.826

1.842

1.823

C-H

1.096

S-H

1.357

N-H

1.033

O-O

1.375

O=O

1.374

P-H

1.418

S=O

1.505

Table 3: Bond Length (Å) variation due to gas adsorption on Mn-BNNS

Bond type

Mn-BNNS

+CH4

Mn-BNNS

+H2S

Mn-BNNS

+ NH3

Mn-BNNS

+O3

Mn-BNNS

+PH3

Mn-BNNS

+SO2

B-N

1.454

1.4537

1.453

1.4536

1.451

1.453

1.451

Mn-N

1.921

1.925

1.947

1.957

1.91

1.947

1.91

C-H

1.095

S-H

1.356

N-H

1.03

O-O

1.378

O=O

1.379

P-H

1.419

S=O

1.536

Adsorption Properties

Table 4: Adsorption energy (eV) and length of the BNNS, Co-BNNS, and Mn-BNNS sheet for

gas molecules

Adsorbed

gas

Adsorption energy (eV)

Adsorption Length (Å)

BNNS

Co-BNNS

Mn-BNNS

BNNS

Co-BNNS

Mn-BNNS

CH4

-0.16

-0.12

-0.14

3.76

2.269

2.314

H2S

-0.26

-0.68

-0.65

3.49

2.335

2.484

NH3

-0.12

-1.26

-0.94

3.94

2.024

2.22

-0.17

-2.96

-3.18

3.179

2.005

2.085

PH3

-0.02

-0.96

-0.88

4.274

2.269

2.44

SO2

-0.18

-1.24

-1.36

3.414

1.954

2.16

Adsorption energy is the interaction energy required to adsorb gas molecules to the surface of the

adsorbent. The adsorption energies were computed and shown in Table 4 along with the associated

adsorption height for various absorbed gases. The adsorption energies are negative for the selected

gases; hence, each of the gas molecules CH4, H2S, NH3, O3, PH3, and SO2 were adsorbed on BNNS,

Co-BNNS, and Mn-BNNS, respectively, among which H2S shows the most substantial interaction with

BNNS whereas, O3 is strongly adsorbed in Co-BNNS and Mn-BNNS compared to all other gases.

All the gases show strong interaction with Mn-BNNS and Co-BNNS compared to BNNS. The

adsorption heights are small for the adsorbent Mn-BNNS and Co-BNNS but large for the BNNS. All

the gases have a higher magnitude of adsorption energy on the designed metal-doped BNNS compared

to graphene, B-doped graphene, boron nitride nanotube, arsenene nanosheet, and so on [5,6,43–46].

However, the adsorption energies of H2S, CH4, and NH3 are weaker on the designed nanosheets than

on WO3 and MoS2 sheets [47,48]. The observed adsorption energies suggest that Co-BNNS and Mn-

BNNS are more suitable than BNNS for the selected gas sensing. The adsorption length of H2S, CH4,

NH3, PH3, and SO2 is comparatively higher on BNNS but lower in Co-BNNS and Mn-BNNS than on

the boron-carbon-nitride structure [19,49,50].

Table 5: Recovery time (s) of different adsorbates in the nanosheets

Adsorbed

gas

BNNS

Co-BNNS

Mn-BNNS

CH4

5.08×10-10

1.07×10-10

2.3×10-10

H2S

2.5×10-8

0.317

0.098

NH3

1.07×10-10

2.04×109

7.9×103

7.5×10-10

1.15×1038

6.06×1041

PH3

2.18×10-12

1.7×104

764.08

SO2

1.11×10-09

9.4×108

1.0×1011

One of the crucial properties, the recovery time of the sensing materials, can be estimated from equation

2 [19],

  





 ,

(2)

where K and T represent Boltzmann's constant (8.617×10-5 eV.K-1) and temperature, respectively.

Experimentally a sensor is recovered by exposing it to UV radiation with a frequency of (fo = 1012 to

3×1014 Hz) at a temperature of 298 to 350 K. In this research, we calculated the recovery time using fo=

1012 Hz and T= 298 K [19]. The recovery time of the pristine BNNS ranges between ~10-12 s to ~10-8 s

(Table 5), whereas it extends to the order of 1038s and 1041s for Co-BNNS and Mn-BNNS due to higher

adsorption energies. The high recovery time of O3 in the Co-BNNS and Mn-BNNS makes it too hard

for practical application.

Electronic Properties

Mulliken Charge Analysis

The charge analysis using the Mulliken population analysis (MPA) [51] indicates that about 0.84e

charges on average are transferred from the B atoms to its adjacent N atoms within the sheet due to

higher electronegativity of the N atom, indicating the partially ionic character of the B–N bonds in the

pristine BNNS. After the adsorption of the gas molecules, the B and N atoms still show partially positive

and negative charges, respectively. The elements (N, C, O, and P) show partially negative charges due

to their electronegativity, suggesting N, C, O, and P are electron acceptors. The S atom shows a partially

negative charge in H2S, whereas there is a partially positive charge in SO2 since the O atom is

comparatively more electronegative than the S atom. Hence the S atom acts as the electron acceptor in

H2S but acts as the electron donor in the SO2 molecule (Table 6).

Being electropositive elements, Co (Table 7) and Mn (Table 8) show the maximum partial positive

charges in the Co-BNNS and Mn-BNNS structure, respectively. The partial positive charge of Co and

Mn increased after gas adsorption, i.e., electrons are pulled toward the electronegative elements of the

gas molecules. The charge distribution of all other elements follows a similar pattern for both doped

nanosheets after adsorption.

Table 6: Mulliken Charge distribution of pristine and gas-adsorbed BNNS

Elements

BNNS

BNNS+CH4

BNNS+H2S

BNNS+NH3

BNNS+O3

BNNS+PH3

BNNS+SO2

0.84

0.835

0.863

0.835

0.837

0.84

0.836

-0.84

-0.835

-0.863

-0.86

-0.832

-0.838

-0.836

0.27

0.19

0.41

0.04

-1.09

-0.026

-0.8

-0.12

--s

-0.38

1.6

Table 7:Mulliken Charge distribution of pristine and gas-adsorbed Co-BNNS

Elements

Co-

BNNS

Co-BNNS

+ CH4

Co-BNNS

+ H2S

Co-BNNS

+ NH3

Co-BNNS

+ O3

Co-BNNS

+ PH3

Co-BNNS

+ SO2

0.79

0.791

0.785

0.769

0.799

0.786

0.798

-0.82

-0.824

-0.823

-0.829

-0.810

-0.822

-0.818

1.28

1.58

1.53

1.56

1.50

1.35

1.39

0.22

0.18

0.403

0.043

-1.0

-0.177

-0.77

-0.12

-0.28

1.25

Table 8: Mulliken Charge distribution of pristine and gas-adsorbed Mn-BNNS

Elements

Mn-

BNNS

Mn-BNNS

+ CH4

Mn-BNNS

+H2S

Mn-BNNS

+ NH3

Mn-BNNS

+ O3

Mn-BNNS

+ PH3

Mn-BNNS

+ SO2

0.795

0.79

0.785

0.783

0.80

0.787

0.797

-0.82

-0.821

-0.822

-0.813

-0.818

-0.812

1.25

1.39

1.30

1.38

1.52

1.32

1.48

0.22

0.17

0.4

0.04

-0.99

-0.18

-0.8

-0.16

-0.31

1.15

Band Gap Analysis

Figure 4 represents the band structure of the pristine BNNS and gas-adsorbed BNNS. All structures

except SO2 + BNNS show an indirect band gap with conduction band minimum (CBM) at G point and

valence band maximum (VBM) at Q point in the K-space. The band gap pristine BNNS is about 4.7 eV

which is analogous to previous studies [52]. The band gap of BNNS decreased after gas adsorption,

among which, after adsorbing O3, the band gap decreased significantly, which satisfies previous

research [53]. According to the band gap study, an insulator-to-semiconductor transition is observed

after O3 and SO2 adsorption. Hence, the BNNS can show a strong electronic response via O3 and SO2

adsorption. For all other complexes, the band gap is very wide.

Figure 4: Band structures of pristine and gas-adsorbed BNNS

Figure 5 represents the band structure of the pure and gas-adsorbed Co-doped BNNS. Since the

conduction band (CB) overlaps with the valance band (VB), an insulator-to-conductor transition is

occurred due to Co doping. After the adsorption of the CH4 molecule, the complex still acts like a

conductor with a zero band gap. However, semiconducting properties arise after the adsorption of the

other gas molecules. Hence, the Co-doped BNNS can offer a significant change in electrical

-6

-4

-2

Band gap= 1.720 eV

Energy (eV)

BNNS + SO2

GFZ

-6

-4

-2

Band gap= 0.292 eV

Energy (eV)

BNNS + O3

G F Z

-6

-4

-2

Band gap= 4.538 eV

Energy (eV)

BNNS + PH3

G F Z

-6

-4

-2

Band gap= 4.531 eV

Energy (eV)

BNNS + H2S

GFZ

-6

-4

-2

Band gap= 4.663 eV

Energy (eV)

BNNS + CH4

GFZ

-6

-4

-2

Band gap= 4.552 eV

Energy (eV)

BNNS + NH3

GFZ

-6

-4

-2

Band gap= 4.725 eV

Energy (eV)

Pristine BNNS

conductivity through the interaction with H2S, NH3, O3, PH3, and SO2 gases, suggesting it to be a

promising material for toxic gas sensing. The indirect band gap arises with CBM at Q point and VBM

at G point.

The Mn-doped BNNS is a direct band gap semiconductor with VBM and CBM located at the Q point

(Figure 6). After gas adsorption, the band gap decreased significantly, i.e., a rise in electrical

conductivity can be observed due to interaction with the toxic gases, which can offer a better gas sensing

ability. Indirect band gaps were observed for the Mn-BNNS+CH4, Mn-BNNS+H2S, Mn-BNNS+NH3,

Mn-BNNS+PH3, and Mn-BNNS+SO2 with VBM at G point and CBM at Q point, whereas Mn-

BNNS+O3 possessed a direct band gap with VBM and CBM at Q point.

Figure 5: Band structures of pristine and gas-adsorbed Co-BNNS

-3

-2

-1

Band gap = 0.647 eV

Energy (eV)

Co-BNNS+SO2

-2

-1

Band gap = 0.258 eV

Energy (eV)

Co-BNNS+O3

-3

-2

-1

Band gap = 0.342 eV

Energy (eV)

Co-BNNS+PH3

-2

-1

Energy (eV)

Co-BNNS + CH4

-2

-1

2Band gap = 0.093 eV

Energy (eV)

Co-BNNS+NH3

-3

-2

-1

3Band gap = 0.155 eV

Energy (eV)

Co-BNNS+H2S

-1

Energy (eV)

Co-BNNS

Figure 6: Band structures of pristine and gas-adsorbed Mn-BNNS

Density of States (DOS)

Figure 7: Total density of states of the pristine and gas-adsorbed nanosheets

The total density of states (TDOS) spectra of pristine and gas-adsorbed BNNS, Co-BNNS, and Mn-

BNNS are given in Figure 7. Occupied and unoccupied molecular orbitals in the scenario of BNNS

-2

-1

3Band gap = 0.558 eV

Energy (eV)

Mn-BNNS+SO2

-2

-1

3Band gap = 0.460 eV

Energy (eV)

Mn-BNNS+PH3

-2

-1

Band gap = 0.437 eV

Energy (eV)

Mn-BNNS-O3

-2

-1

3Band gap = 0.680 eV

Energy (eV)

Mn-BNNS+NH3

-2

-1

Energy (eV)

Band gap = 0.707 eV Mn-BNNS+H2S

-3

-2

-1

Band gap = 1.243 eV

Energy (eV)

Mn-BNNS+CH4

-3

-2

-1

3Band gap = 1.327 eV

Energy (eV)

Mn-BNNS

were far apart, suggesting BNNS to be a wide band gap insulator. New energy levels appeared on doping

the pristine BNNS. As a result, an increased charge transfer to the gas molecules was observed. The

TDOS showed a continuous value near the fermi level for Co-BNNS, suggesting a metallic behavior,

whereas a very small gap between occupied and unoccupied orbitals was observed for Mn-BNNS,

resulting in a semiconductor. A slight variation of DOS near the fermi level of Co-BNNS and Mo-

BNNS is observed after gas adsorption due to the charge transfer from the gas molecules to the

nanosheet, which caused a slight variation in the band gap after adsorption. The TDOS spectra of all

the complexes satisfy their band structures.

Optical Properties

The interaction of light with the complexes is explained by their optical properties, such as energy loss

function (LF), refractive index (η), dielectric function (DF), absorption coefficient (AC), and

reflectivity (R). These optical properties of all the structures are shown in Figure 8-13. The real ()

and imaginary () part of the dielectric function is shown in Figure 8 and Figure 9. The imaginary

component of the dielectric function provides information about how much energy is lost in the

substance, which signifies the absorption of light, whereas the real part of the dielectric function

describes polarization within the structures. From our observation, the imaginary part () gives one

peak at 223 nm for BNNS which showed a very slight shifting of up to 8nm after gas adsorption. For

Co-BNNS and Mn-BNNS, similar peak positions of  is observed. This peak is connected to the inter-

band transition from the valance band to the conduction band. The real part also shows a slight peak

shifting due to gas adsorption. Both the real and imaginary part of the dielectric function of BNNS

satisfies the previous report [54].

Figure 8: Real part of complex dielectric function for BNNS, Co-BNNS, and Mn-BNNS with

toxic gases

100 200 300 400 500 600 700

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Dielectric function (imaginary)

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

Dielectric function (imaginary)

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Dielectric function (imaginary)

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

100 200 300 400 500 600 700

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Dielectric function (real)

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

-1

Dielectric function (real)

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Dielectric function (real)

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

Figure 9: Imaginary part of complex dielectric function for BNNS, Co-BNNS, and Mn-BNNS

with toxic gases

Figure 10: Absorption coefficient for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

The AC pattern is quite similar for all the structures, with a maximum in the ultraviolet energy region

(Figure 10). The AC extends over 105 cm-1 order for all complexes, which suggests that all the structures

absorb UV wavelength very strongly. The absorption nature of the BNNS is analogous to previous

reports [55,56]. The high absorption coefficients make the BNNS, Co-BNNS, and Mn-BNNS potential

material for numerous optoelectronic applications.

The energy first absorbed by material from electromagnetic radiation is the threshold point in the

absorption. This point appears at nearly 200 nm for BNNS & Co-BNNS but 220 nm for Mn-BNNS. A

slight shifting of absorption edge occurred due to the interaction with toxic gases, suggesting a slight

optical response due to gas sensing. Due to the peak shifting and intensity variation, it will be possible

to determine the type of attached toxic gas through optical measurement [57].

Figure 11: Loss function for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

100 200 300 400 500 600 700

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Dielectric function (imaginary)

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

Dielectric function (imaginary)

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Dielectric function (imaginary)

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

100 200 300 400 500 600 700

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Dielectric function (real)

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

-1

Dielectric function (real)

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Dielectric function (real)

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

100 200 300 400 500 600 700

20000

40000

60000

80000

100000

120000

Absorption Coefficient (cm-1)

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

100 200 300 400 500 600 700

20000

40000

60000

80000

100000

120000

140000

160000

Absorption Coefficient (cm-1)

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

20000

40000

60000

80000

100000

Absorption Coefficient (cm-1)

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Loss function

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400

Loss function

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400

Loss function

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

The electron energy loss function, which explains typical plasmonic oscillations, is shown in Figure

11. The fast electrons moving through the material are responsible for its macroscopic and microscopic

features. Energy loss is evident during this phase, and the entire event is closely related to LF. The

plasmon peak is among the most important peaks in the energy loss function spectrum. These peaks

and the atypical peaks of reflectivity are connected.

Figure 12: Reflectivity for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

Regarding wavelength, the optical reflectivity of BNNS, Co-BNNS, and Mn-BNNS with toxic gases

was calculated and shown in Figure 12. The minimum reflectivity is observed for Mn-BNNS compared

to BNNS and Co-BNNS. For BNNS and Co-BNNS, about 35% of the incident energy in the UV region

is reflected. The visible energy loss due to reflection is significantly less for all the complexes. The

reflectivity spectra also showed slight peak shifting and changes in peak intensity after gas adsorption.

Hence the reflected energy can be used to determine the adsorbed gas type [57].

Figure 13: Refractive index for BNNS, Co-BNNS, and Mn-BNNS with toxic gases

The Refractive index is energy-dependent. The highest refractive index value is associated with the

lowest absorption energy for all systems between 250 and 280 nm. Figure 13 makes it clear how the

refractive index continues to drop as absorption increases to higher levels. For all systems, the local

maxima of the real component of the refractive index are correlated with the local maxima of the real

part of the dielectric function. The variation in the refractive index suggests that the speed of the

electromagnetic spectrum in the medium changes after gas adsorption, which can be a way of detecting

the adsorbed gas. The refractive index of BNNS follows the previous research [54].

100 200 300 400 500 600 700

0.00

0.05

0.10

0.15

0.20

0.25

Reflectivity

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

0.0

0.1

0.2

0.3

0.4

Reflectivity

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Reflectivity

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

100 200 300 400 500 600 700

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

Refractive Index

Wavelength (nm)

Mn-BNNS

Mn-BNNS + CH4

Mn-BNNS + H2S

Mn-BNNS + NH3

Mn-BNNS + O3

Mn-BNNS + PH3

Mn-BNNS + SO2

100 200 300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

Refractive Index

Wavelength (nm)

Co-BNNS

Co-BNNS + CH4

Co-BNNS + H2S

Co-BNNS + NH3

Co-BNNS + O3

Co-BNNS + PH3

Co-BNNS + SO2

100 200 300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

Refractive Index

Wavelength (nm)

BNNS

BNNS + CH4

BNNS + H2S

BNNS + NH3

BNNS + O3

BNNS + PH3

BNNS + SO2

Conclusion

The pristine BNNS is successfully doped with Co and Mn and investigated using DFT calculation. The

doping of Co and Mn in BNNS results in significant structural deformation with a remarkable change

in electronic properties. The BNNS transformed into a metal and semiconductor via Co and Mn doping,

respectively. The gas-sensing ability of the three nanosheets (BNNS, Co-BNNS, and Mn-BNNS) are

studied, revealing higher sensitivity of Co-BNNS and Mn-BNNS than pristine BNNS toward hazardous

gases (i.e., CH4, H2S, NH3, O3, PH3, and SO2) with a very high recovery time. Very slight structural

deformation of the nanosheets was observed due to gas adsorption. Both BNNS and Mn-BNNS showed

a reduction of band gap due to adsorption, whereas a slight band gap arises for metallic Co-BNNS after

adsorption, suggesting it to be more suitable for gas sensing applications. The Mulliken change analysis

shows the change distribution in the pristine and gas-adsorbed structures. All the structures show high

absorption coefficients in the UV wavelength region and low refractive index suggesting to be potential

materials for optoelectronic research. The variation in peak intensity and peak position of the reflectivity

or absorption can be used as an optical gas sensor that can detect the type of adsorbed gas based on

optical measurement. Based on the measurement of adsorption energy, electronic band gap, and optical

properties, both Mn and Co-doped BNNS are better candidates for toxic gas sensing compared to pure

BNNS.

Acknowledgment

We are thankful to the Jashore University of Science and Technology Project Grant 2022-2023

for providing the necessary financial support for this research.

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The adsorption of CO gas on the surface of boron nitride incorporating 2D carbon allotropes: a DFT analysis

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The adsorption properties of different Carbon allotropes (i.e., graphene, γ-graphyne, Mobius graphene, and R-graphyne) and their corresponding Boron (N) and Nitrogen (N) incorporated BCN nanostructures toward carbon monoxide (CO) gas are studied via density functional theory calculation. All the adsorbents demonstrated negative formation energies and real frequencies, i.e., can be synthesized and have dynamical stability. The adsorption energies have increased due to B and N incorporation, although still comparatively low for practical application. The highest adsorption energy with suitable recovery time is observed for the Mobius BCN structure, about −0.112 eV and 77.8 ps, respectively. Very nominal charge transfer is observed via Mulliken charge distribution and electrostatic potential map analysis. The changes in energy gap and electrical conductivity are observed due to CO adsorption.

Exploring the sensing potential of Fe-decorated h-BN toward harmful gases: a DFT study

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Gas sensing technology has a broad impact on society, ranging from environmental and industrial safety to healthcare and everyday applications, contributing to a safer, healthier, and more sustainable world. We studied pure and Fe-decorated hexagonal boron nitride (h-BN) gas sensor for monitoring of carbon-based gases using density functional theory (DFT). The calculations utilized the Generalized Gradient Approximation with the Perdew–Burke–Ernzerhof (GGA-PBE) exchange-correlation functional. The novelty of our study lies in the investigation of the adsorption of harmful gases such as carbonyl sulfide, carbinol, carbimide, and carbonyl fluoride on both pure and Fe-decorated h-BN. The deviation in structural, electronic, and adsorption properties of h-BN due to Fe decoration has been studied along with the sensing ability to design said material towards carbon monoxide (CO), carbon dioxide (CO2), carbonyl sulfide (COS), carbinol, (CH4O), carbimide (CH2N2), and carbonyl fluoride (CF2O) gases. Gases such as CO, COS, CH2N2, and CF2O exhibited chemisorption, while CO2, and CH4O exhibited physisorption behavior. The introduction of Fe altered the semiconductor properties of h-BN and rendered it metallic. Enhanced electronic properties were observed due to a robust hybridization occurring between the d-orbitals of Fe-decorated BN and the gas molecules. The extended recovery periods observed for gases, aside from CO2, indicate their adhesive interactions with Fe-decorated h-BN. The reduction in desorption duration as temperature rises allows Fe-decorated h-BN to function as a reversible gas sensor. This research opens up a novel pathway for the synthesis and advancement of cost-effective, environmentally friendly double-atom catalysts with high sensitivity for capturing and detecting molecules such as CO, COS, CH2N2, CO2, CH4O, and CF2O.

A first principles study of RbSnCl 3 perovskite toward NH 3 , SO 2 , and NO gas sensing

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The sensitivity of a RbSnCl3 perovskite 2D layer toward NH3, SO2, and NO toxic gases has been studied via DFT analysis. The tri-atomic layer of RbSnCl3 possessed a tetragonal symmetry with a band gap of 1.433 eV. The adsorption energies of RbSnCl3 for NH3, SO2 and NO are −0.09, −0.43, and −0.56 eV respectively with a recovery time ranging from 3.4 × 10⁻⁸ to 3.5 ms. RbSnCl3 is highly sensitive toward SO2 and NO compared to NH3. The adsorption of SO2 and NO results in a significant structural deformation and a semiconductor-to-metal transition of RbSnCl3 perovskite. A high absorption coefficient (>10³ cm⁻¹), excessive optical conductivity (>10¹⁴ s⁻¹), and a very low reflectivity (<3%) make RbSnCl3 a potential candidate for numerous optoelectronic applications. A significant shift in optical responses is observed through SO2 and NO adsorption, which can enable identification of the adsorbed gases. The studied characteristics signify that RbSnCl3 can be a potential candidate for SO2 and NO detection.

A first-principles investigation of BF3 and ClF3 gas sensing on N-defected AlN nanosheets

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Apr 2024

We conducted theoretical calculations to examine the energetic stability of pristine aluminum nitride (AlN) and N-defected AlN nanosheets, along with their structural, electronic, and optical properties, utilizing density functional theory. Furthermore, we explored the adsorption properties of BF3 and ClF3 toxic gases on both pristine AlN and N-defected AlN nanosheets. Our findings reveal that the N-defect on the AlN nanosheet enhances the gas adsorption energies (−1.354 and −13.263 eV) compared to the pristine AlN nanosheet. Additionally, the absolute value of the bandgap for the N-defected AlN nanosheet increases to 3.032 eV, exceeding the 2.997 eV value of the pristine AlN nanosheet. The gas molecules suffer significant deformation due to their interaction with adsorbents. Upon BF3 gas adsorption, the bandgap of the N-defected AlN nanosheet diminishes to zero. Moreover, the recovery time after gas adsorption on the N-defected AlN nanosheet surpasses that of the pristine AlN nanosheet. Both adsorbents showed a high absorption coefficient of over 10⁴ cm⁻¹ in the UV region. Significant peak shifting in the optical spectra of the N-defected AlN nanosheet was observed due to gas adsorption. The pronounced changes in structural, electronic, and optical properties following toxic gas adsorption suggest that N-defected AlN nanosheets are suitable for the adsorption (dissociation) of BF3 (ClF3) gases.

Boron and oxygen decorated Zn-doped aluminum/boron nitride and graphene/boron nitride heterostructures for the adsorption of phosgene gas: Density functional theory outlook

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Synthesis and characterization of lithium-doped copper zinc tin sulfide (CZTS) thin films

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Dec 2023

The non-toxic nature and remarkable optoelectronic properties of kesterite (Cu2ZnSnS4 and CZTS) make CZTS a potential candidate for solar cell absorber layer material. Since alkali metal doping has shown a performance boost of active layers of solar cells, this work investigates the effects of significant lithium doping on sol-gel-produced CZTS thin films. CZTS- and lithium (Li)-doped CZTS thin films were prepared using the spin coating technique. The variation of structural, morphological, and optical properties of CZTS due to Li-doping has been studied by x-ray diffraction, scanning electron microscopy, and UV–visible spectroscopy techniques. All the synthesized LixCu2−xZnSnS4 (x = 0, 0.2, 0.4, 0.6) films showed fine crystallinity with average crystallite sizes of 4.745, 6.013, 6.255, and 6.404 nm, respectively. The average grain size decreases from 0.336 to 0.310 µm via increasing Li concentration. The inclusion of Li increased the bandgap energy ranges from 1.5 to 1.808 eV. The Li0.6Cu1.4ZnSnS4 thin showed the highest absorption coefficient of 3.505 × 104 cm−1 among all the prepared thin films. A high optical conductivity over 1014 s−1 was observed for CZTS, which further increased with an increased Li concentration. The synthesized structures showed enhanced characteristics suitable for solar cell application.

A-Site Cation Replacement of Hydrazinium Lead Iodide Perovskites by Borane Ammonium Ions: A DFT Calculation

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Dec 2023

Organometallic perovskites have become one of the most common multifunctional materials in optoelectronic research fields. This research studies density functional theory calculation on orthorhombic hydrazinium lead iodide (N 2 H 5 PbI 3 ) perovskite by replacing A‐site cation with a borane ammonium (BH 2 NH 3 ⁺ ) ion. The perovskite showed a significant structural deformation and an orthorhombic to triclinic phase transition due to A‐site ion replacement. The N 2 H 5 PbI 3 perovskite has a band gap of 1.64 eV, suitable for the solar cell absorber layer. The band gap has increased to 2.12 eV after complete A‐site ion replacement. All structures showed a high absorption coefficient over 10 ⁴ cm ⁻¹ in the low wavelength region and an increase in refractive index from 2.5 to 2.75 due to ion replacement. All the structures showed high optical conductivity of 10 ¹⁵ s ⁻¹ order in the blue wavelength region. These new perovskite structures hold the potential to provide a revolution in optoelectronic research.

A first-principles investigation of structural, thermodynamic, electronic, and optical properties of doped 2D ZrNI monolayer

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Phosphorus-doped T-graphene nanocapsule toward O3 and SO2 gas sensing: a DFT and QTAIM analysis

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Full-text available

Feb 2024

Tetragonal graphene nano-capsule (TGC), a novel stable carbon allotrope of sp2 hybridization is designed and doped with phosphorus (P) to study the O3 and SO2 gas sensitivity via density functional theory calculation. Real frequencies verified the natural existence of both TGC and P-doped TGC (PTGC). Both TGC and PTGC suffer structural deformations due to interaction with O3 and SO2 gases. The amount of charge transfer from the adsorbent to the gas molecule is significantly greater for O3 adsorption than SO2 adsorption. The adsorption energies for TGC + O3 and PTGC + O3 complexes are − 3.46 and − 4.34 eV respectively, whereas for TGC + SO2 and PTGC + SO2 complexes the value decreased to − 0.29 and − 0.30 eV respectively. The dissociation of O3 is observed via interaction with PTGC. A significant variation in electronic energy gap and conductivity results from gas adsorption which can provide efficient electrical responses via gas adsorption. The blue/red shift in the optical response proved to be a way of detecting the types of adsorbed gases. The adsorption of O3 is exothermic and spontaneous whereas the adsorption of SO2 is endothermic and non-spontaneous. The negative change in entropy verifies the thermodynamic stability of all the complexes. QTAIM analysis reveals strong covalent or partial covalent interactions between absorbent and adsorbate. The significant variation in electrical and optical response with optimal adsorbent-gas interaction strength makes both TGC and PTGC promising candidates for O3 and SO2 sensing.

DFT study of sensing properties of defected and transition-metal doped V2CF2 towards CH4

Article

Nov 2023
VACUUM

Structural, optical, and electronic properties of boron nitride incorporated mobius carbon nanoribbon: a DFT calculation

Article

Full-text available

Feb 2023
PHYS SCRIPTA

The interesting characteristics of Mobius structure inspired this research to study the effect of Boron-Nitride incorporation on Mobius Carbon (M-CX; X=48, 44, 24, 12, 4, and 0) nanoribbon. The structural stability, vibrational, electronic, and optical properties of M-CX nanoribbons have been studied via density functional theory. The negative formation energy and real vibrational frequency verified the structural stability and natural existence of the M-CX. All the structures showed a high absorption coefficient over 104 cm-1 and a semiconductor to insulator transition with decreasing Carbon concentration in the M-CX structure. The M-C48 structure has the maximum reactivity whereas the M-C0 structure is chemically more stable. The observed optical and electronic studies suggest the structures are potential materials for optoelectronic research.

First-principles investigation of hexagonal boron-carbon-nitride (h-BCN) nanosheet (2D) as gas sensor towards toxic gases (CO, H2S, PH3, SO2, and HCN)

Article

Full-text available

Jan 2021

The adsorption of various toxic gases (CO, ‘H2S’, ‘PH3’, ‘SO2’, and HCN) on a two-dimensional (2D) boron-carbon-nitride (BCN) sheet has been investigated using the first-principles calculation based on density functional theory (DFT). “The adsorption energy, Mulliken charge, density of states (DOS), and band structures have been studied”. “It is observed from DOS and band structures that BCN is conductive”. “The obtained adsorption energies reveal that BCN is sensitive toward the mentioned gas molecules”.

Density functional theory study of Mobius boron-carbon-nitride as potential CH4, H2S, NH3, COCl2 and CH3OH gas sensor

Article

Full-text available

Nov 2022

The interesting properties of Mobius structure and boron-carbon-nitride (BCN) inspired this research to study different characteristics of Mobius BCN (MBCN) nanoribbon. The structural stability and vibrational, electrical and optical properties are analysed using the density functional theory. The gas-sensing ability of the modelled MBCN structure was also studied for methane, hydrogen sulfide, ammonia, phosgene and methanol gases. The negative adsorption energy and alteration of electronic bandgap verified that MBCN is very sensitive toward the selected gases. The complex structures showed a high absorption coefficient with strong chemical potential and 7 ps–0.3 ms recovery time. The negative change in entropy signifies that all the complex structures were thermodynamically stable. Among the selected gases, the MBCN showed the strongest interaction with methanol gas.

In-plane graphene/boron nitride heterostructures and their potential application as toxic gas sensors

Article

Full-text available

Oct 2021

After the successful synthesis of graphene/hexagonal boron nitride (h-BN) heterostructures, research works have been carried out for their plausible real-world device applications. Such 2D nanosheets gain great attention as they have shown promising gas sensing properties due to their high surface-to-volume ratio and unique electronic properties between graphene and h-BN. Herein, we report a first-principles density functional theory investigation of the structural and electronic properties of pristine graphene (PG), pristine BN, and their in-plane heterostructures employing B3LYP and dispersion-corrected van der Waals functional WB97XD with the 6-311G (d, p) basis set. We found that these predicted nanosheets show good structural stability with favorable cohesive energy and the bandgap gradually increases with the increase in the B-N concentration. We have also studied their adsorption properties toward toxic gas molecules (SO 2 and CO). Among these heterostructures, G2BN2 exhibits greater adsorption energy of about À0.237 eV and À0.335 eV when exposed to SO 2 and CO gas molecules, respectively. The electronic properties such as HOMO and LUMO energies, HOMO-LUMO energy gap, Fermi level, work function, and conductivity significantly changed after the adsorption of SO 2 gas on the nanosheets except for PG, whereas these parameters remain almost the same after the adsorption of the CO gas molecule. Mulliken and natural bond orbital (NBO) charge analysis reveals that charge transfer occurs from gas molecules to the nanosheets except when SO 2 is adsorbed onto PG. Although the adsorption energies for CO gas are slightly greater than those for SO 2 gas for these nanosheets, all other investigations such as electronic properties, charge transfer analysis, molecular electrostatic potential (MEP) map, and global indices predict that these nanosheets are good sensors for SO 2 gas than CO gas molecules.

Structure, Properties and Applications of Two‐Dimensional Hexagonal Boron Nitride

Article

Full-text available

Sep 2021
ADV MATER

Hexagonal boron nitride (h‐BN) has emerged as a strong candidate for two‐dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super‐thin h‐BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti‐corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h‐BN followed by a comprehensive account of state‐of‐the‐art synthesis strategies for 2D h‐BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal‐mechanical‐chemical stability of 2D h‐BN, various potential applications of these structures are described. h‐BN is one of the most promising inorganic materials of this century with possible applications ranging from aerospace to medicine. It has emerged as an exotic 2D material in the post graphene era, owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. This review provides an encyclopedic view of the structure, properties, synthesis and applications of h‐BN.

Highly sensitive and selective gas sensors based on nanoporous CN monolayer for reusable detection of NO, H2S and NH3: A first-principles study

Article

Sep 2022
APPL SURF SCI

To explore the possibility of the nanoporous CN (p-CN) monolayers as high-performance gas sensors, the adsorption, electronic properties and gas-sensing performance of various gases on the p-CN monolayers have been studied by first-principles methods. Only NO, SO2, H2S and NH3 have weak chemisorption on the monolayer, which and the physical adsorption of NO2 and C2H4 changed efficiently the electronic properties and work function of p-CN monolayer. The p-CN monolayer towards NO, NH3, and H2S gases has comparatively high sensitivity, while has quite low sensitivity towards other gases. The characteristics on the I-V curves and work function can effectively distinguish various gases. The recovery time for NO, NH3, and H2S is about 4.1 s, 0.27 s, and 0.018 s at 300 K, respectively, which is fairly moderate for the reuse of the CN-based sensor for NO, NH3, and H2S detection. However, the over-short (or over-long) recovery time for NO2 and C2H4 (< 10⁻⁶ s) (or SO2, c. 35 min) gravely hinders the p-CN-based gas sensors for these gases monitoring. Therefore, the p-CN monolayers as reusable gas sensors have high sensitivity and selectivity at room temperature for NO, H2S and NH3 detection.

Molecular dynamic simulations and computational DFT of adsorption performances of malachite green on the metal fluorides in aqueous medium

Article

Aug 2022
J MOL STRUCT

This work focused on the elucidation of the adsorption mechanism of malachite green (MG) on different metal fluorides MF 2 surface (where M=Mg, Mn, Zn or Ni) using DFT and molecular dynamics (MD) simulation. Global and local electronic parameters, dynamic descriptors and radial distribution function (or pair correlation function) g(r) were evaluated and discussed. Results proved that the investigated molecule has a high electron accepting ability which allow it to be adsorbed strongly on the MF 2 surfaces. MD simulations suggest adsorption energies of-340.26,-313.62,-309.08 and-302.82 kcal/mol, respectively, for MgF 2 , ZnF 2 , MnF 2 and NiF 2. These energies are negative, which indicates that the adsorption process is spontaneous in nature. Moreover, it was found that the studied dye is oriented with the ring parallel to the MgF 2 , ZnF 2 and MnF 2 and vertical to the NiF 2 surface. Also, the MD simulations demonstrate that the interactions that occurred during MG adsorption being assigned to a chemical and physical adsorption. This result is confirmed by the radial distribution function (RDF) analysis. Intramolecular interaction is found to be equal to zero for all systems.

Highly Sensitive and Selective Gas Sensors Based on Nanoporous Cn Monolayer for Reusable Detection of No, H2s and Nh3: A First-Principles Study

Article

Jan 2022

Insights on the enhanced nitrogen dioxide sensing using doped boron nitride nanosheets through the quantum chemical studies

Article

Jul 2022
CHEM PHYS

A comprehensive analysis of the effect of different dopant atoms (Cr, Ni, Al, C, Si, O and S) on the sensing capacity of boron nitride nanosheets (BNNs) towards NO2 gas is reported in this study. The calculations were based on the Kohn-Sham density functional theory (KS-DFT) calculations. The quantum chemical analysis was based on the molecular electrostatic potential maps, HOMO-LUMO distributions, DOS plots, Mullikan charges and quantum descriptors were studied. The NO2 positioning over the nanosheets was optimized at CAM_B3LYP/6-31G level of theory. The infrared spectra obtained from the first principle computations indicated a frequency shift for the N-O symmetric stretching vibrations. The computed Mullikan charges showed a charge transfer from nanosheets to NO2. HOMO-LUMO energies and their distributions confirmed the charge transfer. The reactivity descriptors for Cr and Si-doped BNNs suggested their better ability to adsorb NO2 than other nanosheets. The thermodynamics of the sensing was studied using the adsorption energies that ranged between −0.3 to −2.6 eV, confirming the chemical nature of sensing. Overall, the analysis showed that Cr/BNNs and Ni/BNNs exhibited greater sensing activity towards NO2 than the other doped BNNs.

First-principles investigation of hexagonal boron-carbon-nitride (h-BCN) nanosheet (2D) as gas sensor towards toxic gases (CO, H2S, PH3, SO2, and HCN)

Article

Jan 2021

The adsorption of various toxic gases (CO, ‘H2S’, ‘PH3’, ‘SO2’, and HCN) on a two-dimensional (2D) boron-carbon-nitride (BCN) sheet has been investigated using the first-principles calculation based on density functional theory (DFT). The adsorption energy, Mulliken charge, density of states (DOS), and band structures have been studied. It is observed from DOS and band structures that BCN is conductive. The obtained adsorption energies reveal that BCN is sensitive toward the mentioned gas molecules.

First principles investigations of Cobalt and Manganese doped Boron Nitride Nanosheet for Gas Sensing Application

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