Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN nanosheet

Shivam Kansara, Sanjeev K. Gupta, and Yogesh Sonvane

Citation: AIP Conference Proceedings 1961, 030052 (2018); doi: 10.1063/1.5035254

View online: https://doi.org/10.1063/1.5035254
View Table of Contents: http://aip.scitation.org/toc/apc/1961/1
Published by the American Institute of Physics

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 Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN
nanosheet
Shivam Kansara1a), Sanjeev K. Gupta2 and Yogesh Sonvane1
1
Advance Materials Lab, Department of Applied Physics, S.V. National Institute of Technology, Surat 395007, India
2
Computational Materials and Nanoscience Group, Department of Physics and Electronics,
St. Xavier’s College, Ahmedabad 380009, India
a)
Corresponding author: sidkans23@gmail.com

Abstract. We have investigated the electronic properties, adsorptions strength and charge transfer using first principles
calculations using density functional theory (DFT). The hexagonal boron nitride (h-BN) substrate shows metallic
behavior, which helps to enhance the absorption process. The adsorption of three different orientations (S, D and T) of
the H2S gas molecules to analyze the maximum adsorption strength from them onto a copper cluster (Cu4) based on h-BN
nanosheet. The maximum adsorption energy of the H2S gas molecule is -1.50 eV for the S orientation and for D and U, it
is -0.71 eV and -0.78 eV, respectively. The results show that Cu4 cluster helps to capture H2S gas from the environment
and results are useful for the cleaning environment from the toxic gases.

INTRODUCTION
Removing of toxic, corrosive, and odorous gas [1] such as hydrogen sulfide (H2S) from the environment is very
important by chemical method. The H2S derived sulfur dioxide in the combustion process which is responsible for
the acid rain [2]. The adsorption of the H2S gas molecule from the climate has the keynote application in the
industry for waste minimization and pollution control. Nowadays, gas sensing works have a continuous research,
detection of toxic gas is important as the lives for a living [3]. In a little quantity of leakage of toxic gas from
industries can cause harmful which make possible to death. Therefore, the detection of gas has played a significant
role. Two dimensional (2D) hexagonal BN (h-BN) is getting much attention for representing fundamental physics
and auspicious applications in nano-/microscale devices [4]. Due to the lightweight elements and large surface area,
the h-BN substrate is an exciting candidate for a gas sensor, which is due to having band gap and magnetic moment
of defect h-BN [5-6].
Recently, Zhou et al. [7] worked on adsorption of transition metal (TM) (Fe, Co and Ni) on BN sheet and
they have investigated that the magnetic moment is 2.0 μB, 1.0 μB and 0 μB for Fe, Co and Ni, respectively. Deng et
al. [8] have investigated the adsorption of O2, H2, N2, CO, NO, H2O, CO2, NO2, SO2, and NH3 for pure and C-doped
BN sheet and concluded that the adsorption energy in the range of few meV. Here, in this work, we have studied the
structural and electronic properties for different adsorption orientations of the H2S molecule on Cu4 cluster on h-BN
sheet for the application of gas sensors.

International Conference on Nanomaterials for Energy Conversion and Storage Applications

AIP Conf. Proc. 1961, 030052-1–030052-5; https://doi.org/10.1063/1.5035254
Published by AIP Publishing. 978-0-7354-1666-6/$30.00

030052-1
 METHODOLOGY
The hexagonal 3×3×1 BN sheet have been used, where we create a defect by removing one B atoms from the
sheet and adsorb Cu4 cluster exact upon and as shown in Figure 1. The bond distance between B-N and B-B atoms is
approximated 1.37 Å and 1.63 Å, respectively. The angles between N-B-N, B-N-B and B-B-B are 102˚, 136˚ and
120˚. We used Hellmann-Feynman forces criteria smaller than 0.02 eV/Å for the optimizing the structure. The
Kohn-Sham equations were solved using the generalized gradient approximation (GGA) method with the Perdew-
Burke-Ernzerhof (PBE) for PAW exchange-correlation functional [9] as implemented in Vienna Ab initio
Simulation Package (VASP) [10]. We also used van der walls (vdW) interaction in all the calculations. The energy
cut-off for the plane wave expansion was set to 400 eV; a 9×9×1 Monkhorst-Pack grid of k-points was used for
3×3×1 supercell for the structural optimization. The vacuum has been taken 25 Å in the z-direction to remove
interaction from the replication system.

FIGURE 1 The systematic diagram of (a) defected h-BN nanosheet, (b) and (c) show the top and side view of h-BN
nanosheet with adsorbing four atoms of a copper cluster (Cu4). Pink, Blue and Brown colors show the Boron,
Nitrogen and Copper atoms, respectively.

RESULTS AND DISCUSSIONS

(a) Structural properties

The calculated lattice constant for the hexagonal system is a=b=10.73 Å. The total number of atoms in the unit
cell is 35, where we consider one molecule of H2S gas, 4 atoms of Cu, and 28 atoms from BN nanosheet. The bond
length and adsorption energy between Cu and S are 2.25 Å for -1.50 eV, 2.26 Å for -0.71 eV and 2.24 Å for -0.78
eV for orientation A, B and C, respectively. The distance between clusters of gas is different for different
orientation, which is shown in Figure 2. The adsorption energy of the material is calculated using the formula as
follows [11];
E a d s . E co m p lex  E B N  C u  E H S (1)
4 2
Where, E a d s . is the adsorption energy, E c o m p le x , E BN Cu
4
and EH S
2
are the energy of the complex system,
energy of the substrate with Cu cluster and energy of the gas molecule, respectively.

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FIGURE 2 The different adsorption sites of the H2S gas molecule on Cu4 cluster based on h-BN sheet. A, B and C are the
different orientation as S, D and U- sites and also denotes the before and after optimization, respectively.
As per the results, we found that the most favorable adsorption position of H2S on a Cu4 was the A-position. In
other work, the adsorption of H2S gas on the different substrate has been reported with different adsorption energy
where, Ganji et al. [12] reported -0.617 eV and -0.90 eV adsorption values of H2S gas molecules on graphene and
with Au adatom and also -1.317 eV on Au-doped single-walled carbon nanotubes [13]. There are 0.534 eV, -0.0027
eV, 0.0502 eV and -0.0024 eV adsorption values on single-wall carbon nanotubes reported by Oftadeh et al. [14],
which is good comparison with reported work.

FIGURE 3 Electronic charge contours for A, B and C orientations. The charge density has been taken 0.001 e/Å3.

The electron charge density maps of the xz-plane for the unit cells are displayed in Figure 3. It shows directional
last orbital interaction bonds resulting from the delocalized metallic-type interactions. It is also clear from the color
charge density scale that the purple color (+1.0000) comparable to the most extreme charge aggregating site, so the
around atoms have a more prominent charge density than the farther atoms. The comparison of the color of charge
density scales in both structures, which is obvious that the aggregate electronic charge density around the Cu4 cluster
and H2S molecule is very strong. While, the red color range indicate the lack of electrons. The electron transfer for
A, B and C site is 0.0984 |e|, 0.0970 |e| and 0.0982 |e|, respectively. The high adsorption energy is directly relative to
maximum electron transfer between a substrate to gas molecules.
(b) Electronic band structure
The calculated electronic properties for h-BN sheet, h-BN+ Cu sheet and also for different adsorption sites of gas
are shown in Figure 4. The projected density of states and total density of states show the metallic behavior. It is due
to the hybridization before and after adsorption of the gas molecule on a substrate of h-BN with Cu4 cluster. The
projected density of states (PDOS) on an optimal adsorption site (A-sites) was also worked out by first-principles

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calculations for understanding of the influence of H2S gas on the optimal adsorption sites of Cu4 cluster. Due to
adsorption of the H2S molecule, the Fermi level makes more dominant; meanwhile, the electro-conductibility of H2S
adsorbed on a Cu4 surface with B- site was slightly higher than with different sites. It is also found that the
adsorption process was chemisorption, which was caused by intermolecular vdW forces, through contrasting the
distances of a molecule to the Cu4 cluster and the adsorption energies [15, 16].
We also focused the magnetic moment for the highest adsorption A- site. According to the PDOS of the A-
site system, there is no magnetic moment before the adsorption of the H 2S adsorption while after, it makes
magnetized. Here, we take place only last transition orbital of the presented atoms such as p orbital of B, N, S and d
orbital for Cu atom, respectively. The up and down spin contribution at Fermi level, the dominant of the density of
state at down spin and up spin is 17.45 eV and 37.38 eV at Fermi level, respectively (not shown). Using the spin
polarization formula as;
S up  S dow n
P (2)
S up  S dow n
The magnetic moment (PB) of the system is 0.363 PB. In Eqa. (2), Sup and Sdown is the up spin and down spin of the
PDOS.

FIGURE 4 The calculated electronic band structure and total and projected density of states (PDOS) of h-BN sheet,
h-BN+ Cu sheet and complex system of after optimization for all orientation of H2S gas molecule.

CONCLUSIONS
In summary, we have provided insights into the key materials, structural and electronic properties of complex
systems as BN+Cu4+H2S by first principles calculations using DFT. Our calculations show that the toxic gas H2S is
adsorbed on Cu4 cluster with their different orientation and the cohesive energy for each orientation is correlated to
balance the adsorption strengths. The electronic properties such as PDOS show the adsorption behavior of the H2S
molecule after on the surface. Due to the copper cluster, the magnetic moment arises and the value is 0.5 PB. The
maximum adsorption energy is -1.50 eV for the A orientation and for B and C, it is -0.71 eV and -0.78 eV of the gas
molecule. The adsorption of the H2S gas molecule has the applications in a clean climate from the toxic gas
atmosphere.

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