NJC

View Article Online

PAPER
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

View Journal | View Issue

An innovative gas sensor system designed from a

sensitive nanostructured ZnO for the selective
Cite this: New J. Chem., 2017,
41, 12569 detection of SOx molecules: a density functional
theory study
Amirali Abbasi *abc and Jaber Jahanbin Sardroodiabc

The adsorption behaviors of SOx molecules on pristine and N-doped ZnO nanoparticles were investigated
using density functional theory calculations (DFT). The results suggest an improved adsorption ability for
N-doped nanoparticles over undoped nanoparticles. Various adsorption geometries and sites were
considered in detail. In all adsorption sites, the SOx molecule tends to form a bridge geometry with the
ZnO nanoparticle, giving rise to multiple contacting points between the nanoparticle and SOx molecule.
SOx adsorption on the N-doped ZnO nanoparticle is found to be more favorable in energy than the
adsorption on the undoped nanoparticle, suggesting that the N-doped nanoparticles have a higher
sensing capability than the pristine nanoparticles. After adsorption, the S–O bonds of the adsorbed SOx
molecule were stretched, which can be attributed to the transfer of electron density from the S–O bonds
to the newly formed bonds between the ZnO and SOx molecule. The charge analysis based on the natural
bond orbital (NBO) method reveals a considerable charge transfer from the adsorbed SOx molecule to the
ZnO nanoparticle, indicating the donor properties of SOx molecules during the adsorption process.
By analyzing the projected density of states, it was found that chemical bonds were formed between the
Received 14th June 2017, interacting atoms at the interface region. The results also indicate that the electronic densities in the
Accepted 12th September 2017 highest occupied molecular orbitals (HOMOs) were mainly distributed over the SOx molecules, whereas
DOI: 10.1039/c7nj02140b the lowest unoccupied molecular orbitals (LUMOs) were dominant at the ZnO nanoparticle. Our DFT
calculations shed light on the improved adsorption behaviors of N-doped nanoparticles as innovative
rsc.li/njc gas sensors for SOx detection in the environment.

1. Introduction as well as their fundamental application in ZnO based nano-

carriers for drug delivery.2–7 Over the past few decades, numerous
Over the past few years, metal oxide based adsorbents such as research studies have been performed to study the particular
ZnO have been extensively used as effective gas sensors in order properties of ZnO nanoparticles due to their broad applications in
to recognize harmful atmospheric and environmental pollutants. the fields of biomedicine and cancer treatment.8
These oxide semiconductors have been widely investigated due to ZnO has a direct wide band gap ranging from 3.2 to 3.4 eV
their excellent physical and chemical stabilities, low cost, easy and is n-type nature. As a result, the exceptional optical and
availability, and easy synthesis process.1 Among the different electronic properties of ZnO make it a promising material to be
metal oxide semiconductors, nanostructures formed from ZnO utilized in various practical applications such as in solar cells,
have attracted huge interest. ZnO nanoparticles were also gas sensor devices,9 piezoelectric transducers,10 photocatalysts,
demonstrated to be one of the most important candidates for and photovoltaics.11
biomedical applications because of their unique characteristics In addition to the unique electronic and optical properties, it
such as nontoxicity, low cost, biocompatibility and biosafety, can be easily synthesized under controlled chemical conditions
and low temperatures. Furthermore, numerous significant
properties make ZnO an appropriate sensor material for gas
a
Molecular Simulation Laboratory (MSL), Azarbaijan Shahid Madani University, sensing applications including its novel structural arrange-
Tabriz, Iran. E-mail: [email protected]; Tel: +98-412-432-7541
b
ments, high single crystallinity surfaces and increased surface
Computational Nanomaterials research group (CNRG),
Azarbaijan Shahid Madani University, Tabriz, Iran
area to volume ratio. The key functioning principle of metal
c
Department of Chemistry, Faculty of Basic Sciences, oxide based devices is based on the assessment of changes in
Azarbaijan Shahid Madani University, Tabriz, Iran conductivity of the system when a gas molecule adsorbs on

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12569
 View Article Online

Paper NJC

their surfaces. With the development of advanced novel ZnO

nanostructures, especially nanoparticles, their sensing perfor-
mance has been increasingly considered. Particularly, with the
expansion of urban and industrial activities, environmental
protection and management of pollutants in the air have
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

become challenging issues for public health.12

Thus, research on different sensors trying to test toxic gas
molecules has gained a great deal of interest. Metal oxide
semiconductors such as ZnO are of considerable importance
because of their advantages such as low power consumption,
high sensitivity, fast response and rapid recovery. Recently,
many researchers have investigated the sensing behaviors of
ZnO nanomaterials for the detection of harmful gases such as
H2, Cl2, CO, H2O, H2S, NO2, and acetone.13–19
Several theoretical studies on the gas sensing properties of
metal oxide nanoparticles have been published, considering their
adsorption behaviors. For instance, Liu et al. investigated gas
phase CO adsorption on N-doped TiO2 anatase nanoparticles.20
Spencer et al. surveyed the gas sensing applications of Fig. 1 Schematic representation of a typical ZnO gas sensor system for
1D-nanostructured zinc oxide using DFT calculations.21 Moreover, SOx detection.
Tayebee et al. studied the adsorption of aliphatic aldehydes on
ZnO nanoclusters by first principles calculations.22 The adsorp-
analysis method was also considered in this study in order to
tion of NO2 and O3 molecules on the N-doped TiO2 anatase
fully examine the charge exchange between the SOx molecule
nanoparticles has also been investigated in our previous theo-
and the ZnO nanoparticle.
retical works.23,24 Wu et al. performed experiments on sulfur
This work is devoted to the elucidation of reactivity and
dioxide adsorption on ZnO nanoparticles and nanorods.25
adsorption processes that occur at the interface region, being
Performing experimental studies, Singh et al. studied sulfur dioxide
useful in the design and development of highly sensitive devices
and nitrogen dioxide adsorption on zinc oxide and zirconium
for SOx detection in the environment.
hydroxide nanoparticles and the effect on photoluminescence.26
There exists no published paper regarding SO3 adsorption on
the ZnO nanoparticles so far. 2. Computational methods
Our present study sheds light on improving the sensing
behaviors of ZnO nanoparticles for harmful gas detection such 2.1. Details of computation
as SO2 and SO3, caused by nitrogen doping. Sulfur dioxide (SO2) Our calculations were based on the density functional theory29,30
is an important air pollutant with an inactivating role on implemented in the Open source Package for Material eXplorer
catalysts in catalytic reactions. Sulfur trioxide (SO3) as a hazar- (OPENMX3.8).31 OPENMX is an efficient software package for
dous pollutant is also a major component participating in acid nanoscale material simulations, which solves the standard
rain formation. Since SO3 is highly corrosive and hygroscopic, it Kohn–Sham equations.32,33 Pseudoatomic orbitals (PAOs)
can cause severe burns upon both inhalation and ingestion.27 centered on atomic sites were used as basis sets. The basis sets
Thus, the detection of toxic SOx molecules in the environment were created by considering suitable values of pseudoatomic
is a vital issue for public health and human safety. Metal oxide orbitals for the involved atoms. The selected basis sets are
based sensors such as ZnO are generally used as removers or listed as follows: (three-s, three-p, two-d) for the Zn atom,
adsorbents in order to reduce the concentration of these (three-s, three-p) for the S atom and (two-s, two-p) for O and
pollutants to a limited value.28 N atoms, within cutoff radii of basis functions set to the values
A promising gas sensor must be very sensitive to the different of 6 for Zn, 8 for S and 5 for O and N (all in Bohrs). The energy
concentrations of various materials. The selectivity of the sensor cutoff of 150 Ry was utilized for the grid integration to represent
material is also another important factor that should be taken the charge density in the real space. To describe the electronic
into consideration during the design of sensors. ZnO gas sensors exchange and correlation effects, we used the generalized gradient
have been demonstrated to be efficient candidates for harmful approximation (GGA) of Perdew–Burke–Ernzerhof (PBE).34 NBO
gas detection. Fig. 1 presents a schematic representation of charge analysis was also performed in this work in order to
a metal oxide (ZnO) based sensor device for SOx detection in elucidate the charge transfer between the adsorbed molecule and
the environment. We have studied the adsorption of SO2 and ZnO nanoparticle. XCrysDen program35 was used in the display
SO3 molecules on undoped and N-doped ZnO nanoparticles and visualization of the adsorption geometries and isosurfaces
including the electronic density of states and molecular orbitals. of molecular orbitals. The van der Waals interactions between
The structural properties were also discussed in view of the the nanoparticle and SOx molecules were analyzed based on
bond lengths, angles and adsorption energies. The NBO charge the Grimme’s DFT-D2 method.36 However, the long range vdW

12570 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 View Article Online

NJC Paper

interactions were taken into account in order to improve The results of the adsorption energies indicate that the simulated
the adsorption configuration based on the robust and efficient nanoclusters are stable and more energy favorable. We performed
DFT-D methodology. The adsorption energy, DEad, is defined as: our calculations on the ZnO nanoclusters by following Spencer
and co-workers.9,21,43 To eliminate the interaction between the
DEad = E(particle+adsorbate) Eparticle Eadsorbate (1) neighboring particles, a vacuum region of 12.8 Å was set between
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

where Eparticle and Eadsorbate are the total energies of the ZnO and the adjacent images. For the bent geometric structure of the SO2
SOx molecule alone, respectively, while E(particle+adsorbate) is the molecule, the calculated S–O bond length of 1.45 Å and O–S–O
total energy of the particle–SOx system in the equilibrium state. bond angle of 1191 are consistent with the previous theoretical and
SOx molecules were placed at different sites and distances experimental gas phase results of 1.43 Å and 119.51, respectively.
with respect to the considered ZnO nanoparticles. Based on Gas phase SO3 also has a trigonal planar geometry with an S–O
adsorption energy analysis, we found that the adsorption bond length of 1.43 Å and an O–S–O bond angle of 1201, based on
process over the considered systems is exothermic, indicating GGA calculations. All of these calculated values are in reasonable
that the adsorptions are energy favorable. agreement with the previous theoretical and experimental
data.44 The estimated formation energies are about 4.65 eV
2.2. Modeling ZnO nanoparticles and 5.06 eV for undoped and N-doped ZnO, respectively. The
relative stability of the considered ZnO clusters were also dis-
The considered nanoparticles were constructed by setting a
cussed and verified using negative adsorption energies that
3  3  2 supercell of ZnO. The unit cell of ZnO was taken from
represent the fact that the obtained clusters are more energy
the ‘‘American Mineralogists Database’’ webpage37 reported by
favorable. The computational study on ZnO nanoclusters by
K. Kihara.38 As is apparent from the crystal structure of ZnO,
Al-Sunaidi et al. confirms that our considered nanoclusters are
there are two kinds of oxygen atoms represented by threefold
energetically favorable (stable),47 which is mostly attributed to the
coordinated (3f-O) and fourfold coordinated oxygen (4f-O)
negative values of the formation energies. Our calculated values
atoms. The lattice parameters of wurtzite ZnO were calculated
for the formation energies are mostly consistent with the values
to be a = b = 3.2502 Å, c = 5.205 Å, which are in reasonable
reported by other computational studies.45–48
agreement with the experimentally reported data.21 The calcu-
lated Zn–S (2.36–2.40 Å) and Zn–O (2.07–2.13 Å) bond lengths
are within the range of distances obtained by X-ray diffraction
studies for Zn–S and Zn–O bonds in inorganic compounds.39–42
3. Results and discussion
The substitutional N-doped ZnO nanoparticles were made by 3.1. SO2 adsorption on the ZnO nanoparticles
doping a nitrogen atom at both 3f-O and 4f-O sites. Fig. 2 displays The SO2 molecule can coordinate to the ZnO nanoparticle in
the final optimized structures of the pristine and N-doped ZnO different adsorption sites and configurations. Several adsorption
nanoparticles. geometries for the SO2 molecule adsorbed on the pristine and
The considered pristine and N-doped particles were placed in a N-doped nanoparticles are presented here. Fig. 3 shows the
22 Å 18 Å  32 Å box, which is much larger than the size of the
particles. The ZnO nanoparticle contains 90 atoms (45 Zn and
45 O atoms). As a result, the atomic number ratio between Zn and
O atoms is 1 : 1, and the total charge of the particle would be zero.
The studied ZnO nanoclusters were not passivated. In fact, we
examined the adsorption behaviors of non-passivated pristine and
N-doped ZnO for sensing of SOx molecules in the environment.
The adsorption energies remain unaffected upon saturation of
the surface atoms with hydrogen atoms (hydrogen passivation).

Fig. 2 Optimized structures of pristine and N-doped ZnO nanoparticles: Fig. 3 SO2 adsorption geometries on the doped nitrogen, oxygen and zinc
(a) pristine nanoparticle, (b) OC-substituted nanoparticle and (c) OT-substituted sites of undoped and N-doped ZnO nanoparticles, the central sulfur atom of the
nanoparticle. SO2 molecule is coordinated to the doped nitrogen atom of the nanoparticles.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12571
 View Article Online

Paper NJC

adsorption configurations of the SO2 molecule on the undoped The adsorption energies for the adsorption configurations of
and N-doped ZnO nanoparticles. SO2 on the undoped and N-doped ZnO nanoparticles are listed
For the considered adsorption geometries, we can see that the in Table 2. The adsorption energies presented in Table 2 show
central sulfur atom moves toward the nitrogen or oxygen atom of that the studied complexes are energetically favorable with
ZnO, forming strong chemical bonds. Configurations A and B respect to the composite and non-adsorbed SOx. This means
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

show the adsorption of the SO2 molecule on the OC-substituted that they are in a lower energy level and probably are thermo-
and OT-substituted nanoparticles, respectively, whereas configu- dynamically favorable. The relative stability of ZnO–SOx com-
ration C represents SO2 adsorption on the pristine nanoparticle. plexes has also been discussed and verified using negative
For all configurations, we can see that there is a triple contacting adsorption energies that represent the fact that the obtained
point between the nanoparticle and SO2 molecule. The binding clusters are more energy favorable. Recently, several works on
sites for configuration A occur on the zinc and doped nitrogen the stability and optical and structural properties of N-doped
atoms, giving rise to the formation of chemical bonds between the ZnO have been conducted.
SO2 and ZnO nanoparticles. The central sulfur atom was chemi- The results of these studies suggest that the ZnO particles or thin
cally connected to the doped nitrogen atom. In configurations B films doped with nitrogen atoms are of reasonable stability.49–55
and C, the binding sites were located on the zinc and oxygen Thus, we can substitute a nitrogen atom into the ZnO lattice,
atoms of the ZnO nanoparticle, and the oxygen and sulfur atoms and the obtained structures are stable for long term operation
of the SO2 molecule were strongly coordinated to the zinc and as efficient gas sensors.
oxygen atoms, respectively. Bond lengths and angles for the SO2 The results suggest that the adsorption energy of the
molecule adsorbed on the ZnO nanoparticles are listed in Table 1. N-doped configurations (A and B) is higher (more negative)
As can be seen from this table, the S–O bonds of the than the adsorption energy of configuration C. Configuration
adsorbed SO2 molecule were stretched. The reason for this is C represents SO2 adsorption on the pristine nanoparticle.
that the electron density transfers from the S–O bonds to the Therefore, SO2 adsorption on the N-doped nanoparticle is ener-
newly formed bonds between the ZnO nanoparticle and the SO2 getically more favorable than the adsorption on the undoped
molecule, resulting in weakening of the S–O bonds. In all nanoparticle, implying that the N-doped nanoparticles are more
configurations, the O–S–O bond angles of SO2 were decreased sensitive than the undoped nanoparticles for SO2 detection in
after the adsorption process (see Table 2). In configurations the environment. Moreover, the adsorption energy of configu-
A–C, the bond angles’ reduction could probably be attributed ration B (OT-substituted nanoparticle) is more negative than that
to the formation of the new bond between the nitrogen or
oxygen atom of the nanoparticle and the sulfur atom of the SO2
molecule and consequently to the change in sp hybridization of
sulfur in the SO2 molecule to hybridize with higher p contribu-
tion (near-sp2n, n r 2). This leads to an increase in the p
characteristics of the bonding molecular orbitals of sulfur in
the adsorbed SO2 molecule.

Table 1 Bond lengths (in Å) of the SOx molecule adsorbed on the ZnO
nanoparticles

Newly
Complex Zn–O1 Zn–O2 Zn–S N–S formed O–S S–O1 S–O2 S–O3
A 2.11 2.16 — 1.91 — 1.79 1.79 —
B 2.20 2.21 — — 2.0 1.73 1.73 —
C 2.19 2.21 — — 1.96 1.74 1.75 —
D 2.03 — 2.36 1.94 — 1.70 1.71 1.87
E 2.06 — 2.38 — 2.0 1.68 1.69 1.80
F 2.07 — 2.40 — 1.98 1.69 1.69 1.80

Table 2 Adsorption energies (in eV) and charge transfer values (in e) for
the SOx molecule adsorbed on the ZnO nanoparticles

Adsorption Charge
Complex O–S–O energy (DEad) transfer (DQ)
A 114.4 3.03 0.360
B 113.7 3.08 0.367
C 115.1 0.63 0.266
D 113.4–119.5–120 3.12 0.526 Fig. 4 The total density of states (DOS) for ZnO nanocrystals with the
E 114.2–114.5–121.4 3.16 0.546 adsorbed SO2 molecule: (a) configuration A; (b) configuration B; and
F 113.3–115.3–122.6 0.97 0.327 (c) configuration C.

12572 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 View Article Online

NJC Paper
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

Fig. 5 PDOSs for the adsorption complexes of ZnO nanoparticles with adsorbed SO2 molecules: (a–c) configuration A and (d–f) configuration B.

of configuration A (OC-substituted nanoparticle), confirming

that configuration B is an energy favorable adsorption configu-
ration. Thus, the OT-substituted ZnO nanoparticle can react with
the SO2 molecule more efficiently. By considering these results, it
was found that nitrogen doping is conducive to the interaction of
SO2 with ZnO nanoparticles. For SO2 on the pristine (undoped)
ZnO, the calculated adsorption energy is very close to the
reported experimental value (about 0.54 eV).56 The total density
of states (DOS) of ZnO nanocrystals having adsorbed the gas
phase SO2 molecule is presented in Fig. 4.
The biggest difference is the creation of some small peaks in
the energy values ranging from 12 to 10 eV. Therefore, the
DOS for either the valence or conduction bands of ZnO is
significantly influenced upon adsorption of the SO2 molecule.
In order to further investigate the changes in the electronic
structures caused by SO2 adsorption, we presented the pro-
jected density of states (PDOSs) for SO2 molecules adsorbed on
the ZnO nanoparticles (Fig. 5 and 6). In Fig. 5, panels (a–c)
represent the PDOSs for configuration A, whereas (d–f) show
the PDOSs for configuration B. In panels (a, b, d, e), we can see
significant overlaps between the PDOSs of the zinc atoms of the
nanoparticle and oxygen atoms of the SO2 molecule. These high
overlaps are responsible for the formation of the chemical bonds
between them. Panel (c) shows the PDOS plots of the nitrogen
atom of the nanoparticle and the sulfur atom of SO2, indicating
considerable overlaps between their PDOSs. These overlaps are a
good electronic reason for the formation of new N–S and O–S Fig. 6 PDOSs for the adsorption complexes of ZnO nanoparticles with
chemical bonds between the mentioned atoms. adsorbed SO2 molecules: (a–c) configuration C.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12573
 View Article Online

Paper NJC
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

Fig. 7 PDOSs of the nitrogen, sulfur, and oxygen atoms and different p orbitals for adsorption configurations of ZnO with an adsorbed SO2 molecule
(configurations A and B).

Fig. 9 SO3 adsorption geometries on the doped nitrogen, oxygen and

zinc sites of undoped and N-doped ZnO nanoparticles, the central sulfur
Fig. 8 Isosurfaces of the HOMOs and LUMOs and distribution of spin
atom of the SO3 molecule is coordinated to the doped nitrogen atom of
density for the SO2 molecule adsorbed on the undoped and N-doped ZnO
the nanoparticle.
nanoparticles.

In Fig. 6, there are three panels representing the PDOS spectra the PDOSs of the zinc and oxygen atoms, as well as those of sulfur
for configuration C. Similarly, it can be seen from these panels that and oxygen atoms exhibit large overlaps in some energy levels.

12574 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 View Article Online

NJC Paper

These overlaps confirm the formation of chemical bonds

between the interacting atoms. Comparison of the PDOSs of the
oxygen atom of ZnO and the sulfur atom of the SO2 molecule in
Fig. 5 and 6 shows that there is a higher overlap between the
PDOSs of the oxygen and sulfur atoms in panel (f) of Fig. 5
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

(configuration B), while panel (c) of Fig. 6 presents weak PDOS

overlaps compared to panel (f) of Fig. 5. This is in good
agreement with the higher adsorption energy of configuration B
in comparison with configuration C. Furthermore, panel (c) of
Fig. 5 exhibits strong overlaps between the PDOSs of the doped
nitrogen and sulfur atoms of the SO2 molecule, implying that the
sulfur atom of SO2 strongly binds to the doped nitrogen atom.
Fig. 7 represents the PDOSs of the nitrogen, oxygen and
sulfur atoms, along with the different p orbitals of the sulfur
atom of the SO2 molecule.
As can be seen, the PDOSs of the nitrogen and oxygen atoms
of the nanoparticle shows a considerable overlap with the p3
orbital of the sulfur atom of the SO2 molecule. The p1, p2 and p3
orbitals in these figures will be used as generic labels to
indicate the three-p orbitals of the sulfur atom, as denoted by
Px, Py and Pz, respectively. Thus, the Pz orbital of the sulfur
atom represents a higher interaction with the nitrogen/oxygen
atom of the ZnO nanoparticle.
Molecular orbital calculation was also performed in this study in
order to further analyze the SO2 adsorption on the ZnO nanoparticle.
Fig. 8 represents the HOMOs and LUMOs for the adsorption
configurations of ZnO nanoparticles with SO2 molecules.
Fig. 10 The total density of states (DOS) for the ZnO nanocrystal with the
As can be seen from these figures, the LUMOs are dominant
adsorbed SO3 molecule: (a) configuration D; (b) configuration E; and
(c) configuration F. at the ZnO nanoparticle, whereas the electronic densities in the

Fig. 11 Projected density of states (PDOSs) of the zinc, oxygen, sulfur and nitrogen atoms for the SO3 molecule adsorbed on the undoped and N-doped
ZnO nanoparticles: (a–c) configuration D and (d–f) configuration E.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12575
 View Article Online

Paper NJC

HOMOs are strongly distributed over the adsorbed SO2 mole- spectra for configuration E. For configuration F, the PDOSs is
cule. Thus, SO2 adsorption changes the distribution of electro- also displayed in Fig. 12. The substantial overlaps between the
nic densities on the adsorption system, giving rise to significant PDOSs of the zinc and oxygen atoms, as well as oxygen and
variations in the conductivity of the system. nitrogen atoms represent the formation of chemical bonds
between them.
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

3.2. SO3 adsorption on the ZnO nanoparticles In panels (a–c) of Fig. 12, we can see a similar trend of a large
For SO3 adsorption on the ZnO nanoparticles, we considered overlap between the PDOSs of the zinc and oxygen, as well as
three adsorption geometries as marked by adsorption config- sulfur and oxygen atoms. This is an indication of the formation
urations D–F in Fig. 9. of chemical bonds between these atoms.
Configuration D represents the SO3 adsorption on the By comparison of the PDOSs of the oxygen atom of ZnO and
OC-substituted ZnO nanoparticle, whereas configuration E shows sulfur atom of the SO3 molecule in Fig. 11 and 12, we can see a
the adsorption of the SO3 molecule on the OT-substituted nano- similar trend for the PDOS overlaps. As can be seen, there is a
particle. In configuration F, the SO3 molecule interacts with the larger overlap between the PDOSs of the oxygen and sulfur
pristine ZnO nanoparticle. atoms in panel (f) of Fig. 11 (configuration E), compared to
The bond lengths and angles for SO3 molecules adsorbed on panel (c) of Fig. 12. The higher overlaps of the PDOSs of the
the ZnO nanoparticles are summarized in Table 1. interacting atoms in configuration E are consistent with
The results indicate that the S–O bonds of the SO3 molecule the higher adsorption energy of configuration E compared to
were elongated after the adsorption process, which can be configuration F. This large adsorption energy, as well substan-
attributed to the transfer of electronic density from the S–O tial PDOS overlaps confirm that the SO3 molecule was strongly
bonds of the SO3 to the newly formed bonds between the adsorbed on the N-doped ZnO nanoparticle. Besides, panel (c)
nanoparticle and SO3 molecule. The side oxygen atoms interact of Fig. 12 shows noticeable overlaps between the PDOSs of the
with the zinc atoms and the central sulfur atom coordinates to doped nitrogen and sulfur atom of the SO3 molecule, demon-
the oxygen or doped nitrogen atom of the nanoparticle. Simi- strating that a strong chemical bond was formed between the
larly, the binding sites were placed on the zinc atoms. In all sulfur atom of SO3 and doped nitrogen atom. Fig. 13 displays
adsorption configurations, we can see a double contacting
point between the ZnO nanoparticle and SO3 molecule, and
the oxygen and sulfur atoms of SO3 were bonded to the zinc and
oxygen/doped nitrogen atoms. The adsorption energies for the
SO3 molecule adsorbed on the ZnO nanoparticles are listed
in Table 2.
The results indicate that on the N-doped ZnO nanoparticle
(configurations D and E), the adsorption energies are higher
than those of the undoped nanoparticle, suggesting that the
adsorption on the N-doped nanoparticle is more favorable in
energy than the adsorption on the undoped nanoparticle.
In addition, the adsorption energy of configuration E is more
negative than that of configuration D, which indicates that
configuration E is more stable than configuration D. Thus,
of the three configurations, configuration D has the highest
magnitude of adsorption energy, indicating that the N-doped
ZnO nanoparticle strongly interacts with the SO3 molecule.
Our predicted adsorption energy for SO3 on pristine ZnO is
in good agreement with the experimentally reported result of
0.96 eV.56 The total density of states for the SO3 molecule
adsorbed on the ZnO nanocrystals is displayed in Fig. 10.
As can be seen, the adsorption of SO3 induces some distinct
states at the lower-lying valence bands in the energy range
of 12 eV to 10 eV. Thus, the electronic DOS of the ZnO
nanocrystal is considerably affected by SO3 adsorption. How-
ever, both of the mentioned gas molecule adsorptions can lead
to a significant change of DOS near the Fermi level. Conse-
quently, it can be concluded that the adsorption of SO2 and SO3
has a substantial effect on the electronic structures of ZnO. Fig.
11 and 12 show the PDOSs for the SO3 molecule adsorbed on Fig. 12 Projected density of states (PDOSs) of the zinc, oxygen and sulfur
the pristine and N-doped ZnO nanoparticles. Panels (a–c) show atoms for the SO3 molecule adsorbed on the undoped and N-doped ZnO
the PDOSs for configuration D, while (c–f) display the PDOS nanoparticles: (a–c) configuration F.

12576 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 View Article Online

NJC Paper
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

Fig. 13 PDOSs of the nitrogen, sulfur, oxygen atoms and different p orbitals for adsorption configurations of ZnO with the adsorbed SO3 molecule
(configurations D and E).

the PDOSs of the oxygen, doped nitrogen, sulfur atoms and natural population (NP). In NBO analysis, the input atomic
different p orbitals of the sulfur. orbital basis set is transformed via natural atomic orbitals
In panels (c and g) of this figure, there is a significant (NAOs) and natural hybrid orbitals (NHOs) into natural bond
overlap between the PDOSs of the oxygen or the doped nitrogen orbitals (NBOs). Specifically, for large scale system calculations,
atom of the nanoparticle and the p3 orbital of the sulfur atom. one can effectively calculate and analyze natural populations by
Similarly, we can see that there is a strong mutual interaction choosing target atoms, which is an original scheme based on a
between the Pz orbital of the sulfur atom and nitrogen/oxygen truncated cluster method.59
atom of the ZnO nanoparticle. The isosurfaces of the HOMOs The calculated charge transfer values for different adsorp-
and LUMOs for adsorption configurations of the ZnO nano- tion configurations of SO2 and SO3 on the ZnO nanoparticles
particle with SO3 molecules are represented in Fig. 14. are summarized in Table 2. For instance, DQ = 0.360 |e| (e, the
As can be seen, the HOMOs of the adsorption systems are electron charge) for configuration A indicates that the charge
high over the adsorbed SO3 molecule, whereas the electronic was transferred from the SO2 molecule to the ZnO nanoparticle.
densities in the LUMOs seem to be mainly distributed on the In the case of the SO3 adsorption system, the description is the
ZnO nanoparticle. Moreover, the distribution of spin density same as that of SO2 adsorption. The calculated charge transfer
for the SO2 molecule adsorbed on the ZnO nanoparticle shows values of the N-doped configurations are higher than those of
that the magnetization is mainly located over the SO2 molecule. the undoped configurations, supporting the notion that the
nitrogen doping is dominant during the adsorption of SOx over
3.3. NBO charge analysis the ZnO nanoparticles. This is consistent with the fact that the
NBO analysis has been demonstrated to be one of the most adsorption energies of N-doped configurations are larger than
efficient methods for the investigation of covalent bonds and those of the undoped configurations. For SOx adsorption on the
hybridization, providing a precise estimation of the results. The nanoparticle, of the six configurations (A–F), the highest charge
charge transfer between the nanoparticle and SOx molecule was transfers occur in configurations A and D, whereas the lowest
described in detail based on NBO analysis. In the natural bond charge transfers belong to configurations C and F.
orbital (NBO) method developed by Weinhold,57,58 atomic Natural population (NP) analysis was also carried out by
population (or atomic charge) is calculated by using the atom- NBO analysis. The atomic population of each atom was calcu-
ically localized orbitals, natural atomic orbitals (NAO), that is, lated based on the summation over occupation numbers of all

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12577
 View Article Online

Paper NJC

Table 4 Natural atomic charges of the different interacting atoms for SOx
molecules on the ZnO nanoparticles

Configuration 5f-Zn 5f-Zn Doped N S O(SO2) O(SO2) O(ZnO)

SO2 adsorption
A 1.011 1.028 0.970 1.11 0.732 0.738 —
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

B 1.051 0.981 — 1.22 0.744 0.741 0.741

C 1.057 1.053 — 1.22 0.749 0.744 0.886

Configuration 5f-Zn O(ZnO) Doped N S O(SO3)

SO3 adsorption
D 0.95 — 1.07 1.69 0.792
E 1.037 0.883 — 1.80 0.772
F 1.037 0.890 — 1.80 0.769

4. Conclusions
We have investigated the adsorption behaviors of harmful SOx
molecules on pristine and N-doped ZnO nanoparticles by
means of DFT calculations. SOx molecules were positioned at
different sites with respect to the nanoparticle. The S–O bonds
of the SOx molecules were stretched after the adsorption
process, which is mainly attributed to the transfer of electronic
density from the S–O bonds to the newly formed bonds between
the nanoparticle and SOx. Thus, the adsorption process gives
rise to weakened S–O bonds of the adsorbed SOx molecules.
The results suggest that SOx adsorption on the N-doped ZnO
nanoparticle is energetically more favorable than that on the
pristine nanoparticle. The N-doped ZnO strongly interacts with
Fig. 14 Isosurfaces of the HOMOs and LUMOs for the SO3 molecule the SOx molecule. Therefore, nitrogen doping improves the
adsorbed on the doped nitrogen, zinc and oxygen sites of the ZnO
adsorption of SO2 and SO3 molecules on the ZnO nanoparticles.
nanoparticle.
The considerable overlaps between the PDOS spectra of the
interacting atoms show that a chemical bond forms at the
Table 3 Natural atomic population (NP) analysis for SOx molecules interface region between the contacting atoms. By analyzing
adsorbed on the ZnO nanoparticles the HOMO and LUMO isosurfaces, we found that the electronic
densities in the HOMOs were mainly distributed over the
Configuration 5f-Zn 5f-Zn Doped N S O(SO2) O(SO2) O(ZnO)
adsorbed molecule, whereas in the LUMOs, the electronic densities
SO2 adsorption are high at the ZnO nanoparticle. NBO analysis was also performed
A 18.983 18.971 5.972 4.889 6.732 6.738 —
B 18.942 19.018 — 4.780 6.744 6.741 6.891
in this study, which indicated that the oxygen atoms of SOx
C 18.942 18.946 — 4.773 6.749 6.744 6.886 were negatively charged. In contrast, the zinc and sulfur atoms
have positive charges.
Configuration 5f-Zn O(ZnO) Doped N S O(SO3)
SO3 adsorption
D
E
19.068
18.962
—
6.883
6.068
—
4.305
4.199
6.792
6.772
Conflicts of interest
F 18.962 6.890 — 4.195 6.769
There are no conflicts to declare.

the natural atomic orbitals (NAOs) corresponding to a given

atom. The results of NP calculation are listed in Table 3. Acknowledgements
Natural atomic charges of the different interacting atoms
This work is supported by the Azarbaijan Shahid Madani
including zinc, doped nitrogen, oxygen and sulfur atoms are
University.
listed in Table 4. The results show that the oxygen atoms of the
SOx molecule were negatively charged, while the zinc atoms
have positive charges. The oxygen atoms preferentially coordi- References
nate to the zinc atoms.
The sulfur atom of the SOx molecule possesses a positive 1 Z. L. Wang, J. Phys.: Condens. Matter, 2004, 16, R829.
charge and coordinates to the negatively charged doped nitrogen 2 A. Nel, T. Xia, L. Madler and N. Li, Science, 2006, 311,
or oxygen atoms of the ZnO nanoparticle. 622–627.

12578 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
 View Article Online

NJC Paper

3 S. Rakshit and S. Vasudevan, J. Phys. Chem. C, 2008, 112, 27 N. Tasinato, A. P. Charmet, P. Stoppa, S. Giorgianni and
4531–4537. G. Buffa, Spectrochim. Acta, Part A, 2014, 118, 373–379.
4 D. S. Bohle and C. J. Spina, The Relationship of Oxygen 28 R. Hummatov, O. Gulseren, E. Ozensoy, D. Toffoli and
Binding and Peroxide Sites and the Fluorescent Properties H. Ustunel, J. Phys. Chem. C, 2012, 116, 6191–6199.
of Zinc Oxide Semiconductor Nanocrystals, J. Am. Chem. 29 P. Hohenberg and W. Kohn, Phys. Rev., 1964, 136, B864.
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

Soc., 2007, 129, 12380–12381. 30 W. Kohn and L. Sham, Phys. Rev., 1965, 140, A1133.
5 H. M. Xiong, Y. Xu, Q. G. Ren and Y. Y. Xia, J. Am. Chem. 31 The code, OPENMX, pseudoatomic basis functions, and
Soc., 2008, 130, 7522–7523. pseudopotentials are available on a web site http://www.
6 H. Wang, D. Wingett and M. H. Engelhard, J. Mater. Sci.: openmxsquare.org.
Mater. Med., 2009, 20, 11–22. 32 T. Ozaki, Phys. Rev. B: Condens. Matter Mater. Phys., 2003,
7 S. Dhobale, T. Thite and S. L. Laware, J. Appl. Phys., 2008, 67, 155108.
104, 094907. 33 T. Ozaki and H. Kino, Phys. Rev. B: Condens. Matter Mater.
8 C. Hanley, J. Layne and A. Punnoose, Nanotechnology, 2008, Phys., 2004, 69, 195113.
19, 295103. 34 J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett.,
9 M. J. S. Spencer and I. Yarovsky, J. Phys. Chem. C, 2010, 1981, 78, 1396.
114(24), 10881. 35 A. Koklj, J. Comput. Mater. Sci., 2003, 28, 155–168.
10 J. Shi, M. B. Starr, H. Xiang, Y. Hara, M. A. Anderson, 36 S. Grimme, J. Comput. Chem., 2006, 27, 1787–1799.
J.-H. Seo, Z. Ma and X. Wang, Nano Lett., 2011, 11, 5587. 37 Web page at: http://rruff.geo.arizona.edu/AMS/amcsd.php.
11 L. Li, T. Zhai, Y. Bando and D. Golberg, Nano Energy, 2012, 38 K. Kihara and G. Donnay, Can. Mineral., 1985, 23, 647–654.
1, 91. 39 Comprehensive Coordination Chemistry, ed. G. Wilkinson,
12 S. P. Oberegger, O. A. H. Jones and M. J. S. Spencer, Comput. R. D. Gillard and J. A. McCleverty, Pergamon Press,
Mater. Sci., 2017, 132, 104–115. New York, 1987, ch. 16, p. 56.
13 S. N. Das, J. P. Kar, J. H. Choi, T. I. Lee, K. J. Moon and 40 H. Sellers and E. Shustorovich, Surf. Sci., 1996, 346, 322.
J. M. Myoung, J. Phys. Chem. C, 2010, 114, 1689. 41 H. Sellers and E. Shustorovich, Surf. Sci., 1996, 356, 209.
14 A. Joshi, D. K. Aswal, S. K. Gupta, J. V. Yakhmi and 42 A. F. Wells, Structural Inorganic Chemistry, Oxford University
S. A. Gangal, Appl. Phys. Lett., 2009, 94, 103115. Press, New York, 1987.
15 S. K. Youn, N. Ramgir, C. Y. Wang, K. Subannajui, 43 M. J. S. Spencer, K. W. J. Wong and I. Yarovsky, Surface
V. Cimalla and M. Zacharias, J. Phys. Chem. C, 2010, defects on ZnO nanowires: implications for design of
114, 10092. sensors, J. Phys.: Condens. Matter, 2012, 24, 305001.
16 A. Erol, S. Okur, B. Comba, O. Mermer and M. C. Arikan, 44 W. F. Schneider, J. Phys. Chem. B, 2004, 108, 273–282.
Sens. Actuators, B, 2010, 145, 174. 45 A. Sarsari, S. Javad Hashemifar, H. Salamati and
17 Z. T. Liu, T. X. Fan, D. Zhang, X. L. Gong and J. Q. Xu, Sens. H. Akbarzadeh, J. Phys.: Condens. Matter, 2012, 24, 505502.
Actuators, B, 2009, 136, 499. 46 R. Bovhyra, D. Popovych, O. Bovgyra and A. Serednytski,
18 R. Ferro, Sens. Actuators, B, 2009, 143, 99. Nanoscale Res. Lett., 2017, 12(76), 1–6.
19 Y. Zeng, T. Zhang, M. X. Yuan, M. H. Kang, G. Y. Lu, 47 A. A. Al-Sunaidi, A. A. Sokol, C. R. A. Catlow and S. M. Woodley,
R. Wang, H. T. Fan, Y. He and H. B. Yang, Sens. Actuators, J. Phys. Chem. C, 2008, 112, 18860–18875.
B, 2009, 143, 93. 48 B. Wang, X. Wang and J. Zhao, J. Phys. Chem. C, 2010, 114,
20 J. Liu, L. Dong, W. Guo, T. Liang and W. Lai, J. Phys. 5741–5744.
Chem. C, 2013, 117, 13037–13044. 49 A. B. Lavand and Y. S. Malghe, Synthesis, characterization
21 M. J. S. Spencer, Prog. Mater. Sci., 2012, 57, 437–486. and visible light photocatalytic activity of nitrogen-doped
22 R. Tayebee, N. Zamand, A. Hosseini-nasr and M. Kargar zinc oxide nanospheres, J. Asian Ceram. Soc., 2015, 3(3),
Razi, J. Mol. Struct., 2014, 1065–1066, 135–142. 305–310.
23 A. Abbasi and J. J. Sardroodi, N-doped TiO2 anatase nano- 50 K. Jindal, M. Tomar, R. S. Katiyar and V. Gupta, Structural
particle as a highly sensitive gas sensor for NO2 detection: and magnetic properties of N doped ZnO thin films, J. Appl.
insights from DFT computations, Environ. Sci.: Nano, 2016, Phys., 2012, 111(10), 102805.
3, 1153–1164. 51 X. Sha, F. Tian, D. Li, D. Duan, B. Chu, Y. Liu, B. Liu and
24 A. Abbasi and J. J. Sardroodi, Comput. Theor. Chem., 2016, T. Cui, Ab initio study on the stability of N-doped ZnO under
1095, 15–28. high pressure, RSC Adv., 2015, 5, 16774–16779.
25 C. M. Wu, J. Baltrusaitis, E. G. Gillan and V. H. Grassian, 52 R. Kumari, A. Sahai and N. Goswami, Effect of nitrogen
Sulfur Dioxide Adsorption on ZnO Nanoparticles and doping on structural and optical properties of ZnO
Nanorods, J. Phys. Chem. C, 2011, 115, 10164–10172. nanoparticles, Prog. Nat. Sci.: Mater. Int., 2015, 25(4),
26 J. Singh, A. Mukherjeea, S. K. Sengupta, J. Im, G. W. 300–309.
Peterson and J. E. Whitten, Sulfur dioxide and nitrogen 53 N. P. Herring, L. S. Panchakarla and M. Samy El-Shall,
dioxide adsorption on zinc oxide and zirconium hydroxide P-Type Nitrogen-Doped ZnO Nanostructures with Controlled
nanoparticles and the effect on photoluminescence, Appl. Shape and Doping Level by Facile Microwave Synthesis,
Surf. Sci., 2012, 258, 5778–5785. Langmuir, 2014, 30(8), 2230–2240.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017 New J. Chem., 2017, 41, 12569--12580 | 12579
 View Article Online

Paper NJC

54 Z. Xian-Wei, G. Xiao-Yong and C. Xian-Mei, Microstructure and molecular orbital studies, J. Phys. Chem. B, 1998, 102,
and optical properties of nitrogen-doped ZnO film, Chin. 7033–7043.
Phys. B, 2013, 22(2), 024202. 57 A. E. Reed, L. A. Curtiss and F. Weinhold, Chem. Rev., 1988,
55 F. Stavale, L. Pascua, N. Nilius and H. J. Freund, Lumines- 88, 899–926.
cence Properties of Nitrogen-Doped ZnO, J. Phys. Chem. C, 58 E. D. Glendening, C. R. Landis and F. Weinhold,
Published on 13 September 2017. Downloaded by Indian Institute of Technology Kharagpur on 4/7/2025 4:00:39 PM.

2014, 118, 13693–13696. Wiley Interdiscip. Rev.: Comput. Mol. Sci., 2012, 2(1), 1–42.
56 S. Chaturvedi, J. A. Rodriguez, T. Jirsak and J. Hrbek, 59 T. Ohwaki, M. Otani and T. Ozaki, J. Chem. Phys., 2014,
Surface Chemistry of SO2 on Zn and ZnO: photoemission 140, 244105.

12580 | New J. Chem., 2017, 41, 12569--12580 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017