Colloid and Interface Science Communications 60 (2024) 100784

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Colloid and Interface Science Communications

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Rapid Communication

Selective adsorption and sensing mechanism of ZnFe2O4 (111) surface

towards toxic gases:A first-principles study
Renchu Zhao a, Dachang Chen a, *, Jie Li a, Qing Miao a, Ke Liu a, Beibei Xiao b
a
School of Electrical and Electronic Engineering, Wuhan Polytechnic University, Wuhan 430023, China
b
School of Energy and Power Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China

A R T I C L E I N F O A B S T R A C T

Keywords: ZnFe2O4 possesses an excellent gas-sensing performance, but its sensing mechanism towards different toxic gas
Density functional theory molecules requires further exploration. In this study, the competitive adsorption and sensing properties of several
Toxic gases toxic gases (NO2, NO, SO2, CO, H2S, and NH3) on the ZnFe2O4 (111) surface were investigated using density
ZnFe2O4 (111) surface
functional theory (DFT) calculations. The adsorption energy, charge transfer (QT), occupation function,
Gas sensors
adsorption free energy, charge density difference (CDD), and density of states (DOS) were compared. The results
Sensing mechanism
Selective adsorption reveal that the ZnFe2O4 (111) surface exhibits obvious adsorption for NH3, H2S, NO2, and H2O, besides the
selectivity of NH3 molecule is highest. Strong chemical interactions exist between these harmful gas molecules
and the ZnFe2O4 (111) surface. This study offers valuable theoretical insights into the selective adsorption and
sensing mechanism, contributing to the development of high-performance gas sensors to detect toxic gases.

1. Introduction investigated as potential gas sensing materials due to their abundance,

Toxic gases, such as CO, NO, NO2, H2S, SO2, and NH3, pose severe
threats to the health of human and animal lives. CO, an odorless and
colorless toxic gas, is emitted from automobile exhaust and the com­
bustion of household fuels. It binds to hemoglobin in the blood at a much
faster rate than oxygen, and even trace amounts of inhalation can cause
severe oxygen deprivation damage [1]. Nitrogen compounds such as NO
and NO2 can cause significant harm to the respiratory system [2]. Sulfur
gases, H2S and SO2, are emitted from petroleum and industrial pro­
cesses. H2S is corrosive and flammable at low concentrations and is
considered a toxic, flammable, and highly poisonous gas with harmful
odors resembling rotten eggs, posing a significant health hazard [3]. SO2
is colorless, has a strong irritating odor, and is a major contributor to the
formation of acid rain. NH3 can affect the immune system when exposed
to large amounts [4]. Due to the emission of these harmful gases, air has
been contaminated every day. Therefore, it is crucial to monitor air
quality using efficient gas sensors to protect the environment and
humans from the impact of these harmful gases. In addition, detecting
harmful gases has significant implications for agriculture, food safety,
and electrical engineering equipment monitoring.
Gas sensors based on metal oxide semiconductors, such as SnO2
[5,6], ZnO [7,8]，WO3 [9] and ZnFe2O4 have been extensively
low cost, and ease of preparation. Among MOS materials, ZnFe2O4
nanoparticles, a type of spinel-type ternary metal oxide N-type semi­
conductor, have attracted significant attention due to their high mag­
netic conductivity, non-toxicity, excellent gas sensing performance,
phase stability, and high conductivity, making them a promising gas
sensing material [10]. It has been found that ZnFe2O4 nanoparticles
exhibit sensing activity towards both organic gases, such as acetone [11]
and ethanol [12], as well as inorganic gases, including H2S [13]、O3
[14] and NO2 [15]. ZnFe2O4 has been found to exhibit better sensing
performance compared to single-metal oxide ZnO and Fe2O3. Gao et al.
successfully synthesized porous ZnFe2O4 nanosheets and investigated
their gas sensing properties towards H2S gas using experimental
methods. The results revealed that ZnFe2O4 nanosheets exhibited su­
perior gas sensing performance towards H2S, including higher response
speed, faster response and recovery time, good selectivity, repeatability,
and long-term stability, even at lower operating temperatures (85 ◦ C)
[13]. Moreover, ZnFe2O4 has exhibited sensitivities to ethanol and
acetone that are one and two orders of magnitude higher, respectively,
than those of single-metal oxides [12].
Pervious study constructed the molecular models of adsorption sys­
tems and calculated the geometry, energy, and charge parameters via
DFT based on the first-principles, and the sensing mechanism was

* Corresponding author.
E-mail address: dcchen.wuhan@outlook.com (D. Chen).

https://doi.org/10.1016/j.colcom.2024.100784
Received 15 January 2024; Received in revised form 22 March 2024; Accepted 25 March 2024
Available online 1 April 2024
2215-0382/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
R. Zhao et al.
profoundly discussed [16]. DFT theoretical calculations can provide an
in-depth interpretation of the experimental results. Through combining
experimental investigation with DFT calculations, it can be better
demonstrated that the new gas-sensitive materials hold an excellent
sensing potential [17–19]. In this research, the DFT simulation was used
to clarify the sensing mechanism and the selective adsorption of
ZnFe2O4 (111) surface towards several toxic gases. Zou et al. conducted
DFT calculations to investigate the adsorption of NH3 on the ZnFe2O4
surface and discovered a strong interaction between NH3 gas molecule
and the Zn atoms on the adsorption surface [20]. Regiane et al. com­
bined experimental and DFT calculations to explore different surfaces of
ZnFe2O4 and discussed their gas sensing capabilities towards ozone
molecules, revealing the micro gas-sensing mechanism of O3 [14]. Meng
et al. synthesized ZnFe2O4 nanocubes with exposed (111) crystal sur­
faces using a solvothermal method and demonstrated that the ZnFe2O4
(111) surface exhibited excellent gas sensing activity towards ethanol,
acetone, and triethylamine. They confirmed that the ZnFe2O4 (111)
surface is an active crystal face for sensitive reactions and that the un­
saturated Zn3C atoms are active sites for sensitive reactions [21].
Therefore, enhancing the exposure ratio of the ZnFe2O4 (111) surface
will improve the gas sensing properties of ZnFe2O4 towards specific
target gases. Nonetheless, there is currently a lack of theoretical research
on the adsorption of gas molecules on the ZnFe2O4 (111) surface,
particularly regarding the microscopic interaction between gas mole­
cules and the ZnFe2O4 (111) surface, as well as the selective adsorption
of ZnFe2O4 (111) surface towards different gas molecules. Thus, a more
thorough and detailed exploration of the sensing mechanism from a
physical and chemical perspective is warranted.
In this study, using DFT calculations, Eads, QT, occupation function,
adsorption free energy, CDD, and DOS of adsorption systems were
calculated to theoretically investigate the selective adsorption and
sensing properties of the ZnFe2O4 (111) surface towards different
harmful gas molecules. The outcomes suggest that NO2, H2S, NH3, and
H2O gas molecules have stronger adsorption on the ZnFe2O4 (111)
surface, with NH3 having the highest adsorption energy of − 1.28 eV.
The ZnFe2O4 (111) surface has the highest selectivity towards NH3 and
the lowest selectivity towards NO and CO. The analysis of adsorption
free energy indicates that as the temperature increases, gas molecules
are more likely to desorb, with the NH3 adsorption system being the
most stable at room temperature. The charge transfer of the NO2, H2S,
NH3, and H2O adsorption systems are significant. DOS analysis reveals
strong chemical interactions between the adsorbed gas molecules (NO2,
H2S, NH3, and H2O) and the ZnFe2O4 (111) surface. This study provides
guidance for the design and development of ZnFe2O4 gas sensors to
detect noxious exhaust.
2. Computational details
In this study, the DFT calculations were performed using the DMol3
package. To address electron exchange and correlation functionals, a
generalized gradient approximation (GGA) with the Perdew-Burke-
Ernzerhof function (PBE) was employed [22]. DFT semi-core pseudo­
potential (DSSP) method was implemented to determine the relativistic
effects, in which core electrons were substituted with a single effective
potential [23]. To understand Van der Waals forces and long-range in­
teractions, we incorporated the DFT-D2 method developed by Grimme
[24]. For geometric optimization, the Monkhorst-Pack grid k-point mesh
was set to 3 × 3 × 1, and for electronic structure calculations, a denser
mesh of 3 × 3 × 1 was utilized [25]. During the geometric optimization
process, 1.0 × 10− 6 Ha (1 Ha = 27.212 eV), 0.001 Ha/Å, and 0.005 Å for
energy tolerance, maximum force and maximum displacement were set
for convergence, respectively. To ensure accurate results for total energy
in consideration of static electronic structure, a self-consistent loop en­
ergy of 5.0 × 10− 7 Ha, a global orbital cut-off radius of 5.0 Å and a
smearing of 0.005 Ha were employed [26].
The geometric optimization of the solid-phase crystal cell structure
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Colloid and Interface Science Communications 60 (2024) 100784
of ZnFe2O4 was firstly carried out, and the cell parameters a = b = c =
8.44 Å and α = 90◦ , β = 90◦ , γ = 90◦ were obtained. These optimized cell
parameters for ZnFe2O4 were found to be consistent with previous
experimental data [27], confirming its space group as FD-3 M. Subse­
quently, sections of the ZnFe2O4 crystal cell were cut to obtain the
ZnFe2O4 (111) surface. For calculations involving adsorption properties
and electron structure, a = 11.94 Å, b = 11.94 Å and α = 90◦ , β = 90◦ , γ
= 120◦ were used with a vacuum region of 15 Å to prevent the in­
teractions from adjacent unit [28]. The bottom three layers were con­
strained before proceeding with geometric optimization, and the first
top layer was fully relaxed. Each gas molecule was put upon the surface
with a different initial position. The calculation formula of adsorption
energy (Eads) of each gas molecule adsorbed on ZnFe2O4 (111) surface is
as follows [29]:
Eads = Egas/sub − Esub − Egas (1)
In Eq. (1), the Egas/sub is the total energy of each gas molecule
adsorbed on ZnFe2O4 (111) surface. Esub and Egas represent the calculated
energies of the ZnFe2O4 (111) surface and of isolated gas molecule,
respectively. Eads < 0 means that the process of gas adsorption can be
defined as a spontaneous exothermic reaction. Meanwhile, gas adsorp­
tion can be considered as chemical adsorption when the value of Eads is
less than − 0.6 eV [30]. To study the charge transfer between each gas
molecule and the ZnFe2O4 (111) surface, the Hirsheld analysis was
employed. Charge transfer (QT ) is the difference between the charges
carried by the gas molecule before and after being adsorbed by the
monolayer. A positive value of QT implies that the electrons transfer
from gas molecule to ZnFe2O4 (111) surface, while a negative value
of QT implies that the electron trajectory is reversed. The calculation
formula of QT is as follows [31]:
QT = Qafter − Qbefore (2)
Where, Qafter represents the charge of these gas molecule after
adsorption; Qbefore denotes the charge of gases molecule before adsorp­
tion. To understand the physical and chemical interactions between the
adsorbed gas molecule and the ZnFe2O4 (111) surface, the charge den­
sity, and DOS were calculated and analyzed. After calculating the charge
density, the CDD can be calculated using the following Eq. [29]:
Δρ = ρgas/sub − ρsub − ρgas (3)
Where, ρgas/sub , ρsub and ρgas are the total charge density of the opti­
mized adsorption systems, ZnFe2O4 (111) surface, and isolated gas
molecule, respectively.
3. Results and discussion
3.1. Optimized structure of ZnFe2O4 and ZnFe2O4 (111) surface
The bulk phase crystal structure of zinc ferrite after geometric opti­
mization is presented in Fig. 1(a). The cell parameters are in good
agreement with previous experimental data [27]. Fig. 1(b) displays the
antiferromagnetic properties of the optimized ZnFe2O4 crystal cell, the
black arrows pointing upwards represent the spin state of the Fe atoms
being up, while the green arrows pointing downwards mean the spin
state of the Fe atoms being down. The calculated results indicate that the
spin values (all 3.57) and spin directions of the 16 Fe atoms in the
ZnFe2O4 crystal cell relatively match the previous report (3.7–3.9 using
GGA function) [27]. This consistency suggests that the geometric
structure and calculation method employed in constructing the ZnFe2O4
are reliable. Once the reliability of the ZnFe2O4 crystal cell was ensured,
the ZnFe2O4 (111) surface was obtained through surface cutting.
The optimized structure of the ZnFe2O4 (111) surface is shown in
Fig. 1(c) and (d). Form the top view and side view, there are four Zn3C
atoms on the ZnFe2O4 (111) surface, all located in the first surface layer.
This arrangement facilitates complete contact with the target gases.
R. Zhao et al. Colloid and Interface Science Communications 60 (2024) 100784

Fig. 1. (a) Schematic representation of conventional unit cell of bulk ZnFe2O4 structure; (b) Schematic representation of AFM magnetic model of Fe atoms in bulk
ZnFe2O4 (The arrows indicate the spin direction of these Fe atoms.); (c) Top view of ZnFe2O4(111) optimized structure; (d) front view of ZnFe2O4(111). Thin line
atoms were fixed, while solid atoms were sufficiently relaxed in (c) and (d).

Furthermore, previous studies have demonstrated that the Zn3C atoms

Table 1
on the ZnFe2O4 (111) surface serve as the active centers for adsorption
The adsorption energy, electron transfer and distances between gas molecules
and sensing [21]. Accordingly, the primary objective of this investiga­
and ZnFe2O4 (111) surface.
tion is to uncover the adsorption mechanism, selectivity analysis, and
System Eads (eV) QT (e) (Hirsheld) Distances(Å)
electronic properties of Zn3C towards various gases.
The optimized structures of the adsorption of toxic gas molecules NO2 − 0.75 − 0.20 (O–Zn)2.04
(with N2, O2, and H2O as background gas) on the ZnFe2O4 (111) surface SO2 − 0.68 − 0.04 (O–Zn)2.12 (S–O)2.25
H2S 0.83 0.20 (S–Zn)2.51 (H–O)2.19
were obtained, and the structures with a large adsorption energy are
−
NH3 − 1.28 0.14 (N–Zn)2.10
shown in Fig. 2. The Eads, QT, and adsorption distances of adsorption H2O − 0.76 0.19 (H–Zn)2.17
systems are listed in Table 1.
The highest adsorption energy is observed for NH3 molecule on the
ZnFe2O4 (111) surface, with a value of − 1.28 eV. For the NO2 and SO2 3.2. Selective adsorption analysis of the ZnFe2O4 (111) surface
adsorption systems, two adsorption orientations of the gas molecules
were considered. The adsorption energy results reveal that NO2 tends to Typically, the composition of under test gases comprises diverse
adsorb with the O atom facing downward on the ZnFe2O4 (111) surface, harmful gas molecules and N2, O2, and H2O molecules, necessitating the
with an adsorption energy of − 0.75 eV, which is higher than the selective analysis of gas molecules for accurate detection. This selective
adsorption energy corresponding to the N atom facing downward. adsorption analysis not only unveils the competitive adsorption
Similarly, the adsorption energy of SO2 with the S atom facing down­ behavior of various gas molecules, but also helps determine the optimal
ward is − 0.68 eV, which is greater than the adsorption energy of the operating temperature of the gas sensors. In this study, the occupation
adsorption system with the O atom facing downward. function was employed to assess the selectivity of the ZnFe2O4 (111)
It’s worth noting that the adsorption energies of O2 and N2 are − 0.21 surface towards various gases. The calculation formula of occupation
eV and − 0.24 eV (listed in Table S1), respectively, both of which are less function value was given as follow [32]:
than − 0.30 eV. This indicates weak adsorption between these two gas
Ngas eNgas [μgas (P,T)− Egas ]/kB T
ads

molecules and the ZnFe2O4 (111) surface. The order of adsorption en­
ergies for toxic gases and background gas molecules on the ZnFe2O4
(111) surface is as follows: NH3 > H2S > H2O > NO2 > SO2 > CO > NO >
O2 .
fgas (P, T) = ∑ (4)
1 + xi Nxi eNxi [μxi (P,T)− Exi ]/kB T
ads
Where, xi represents a certain gas molecule, Nxi is the number of gas
molecules captured at a unit point. One active site can only adsorb one

Fig. 2. Optimized structure of several gas molecules after adsorption on the ZnFe2O4 (111) surface (a) NO2; (b) SO2; (c) H2S; (d) NH3; (e) H2O.

3
R. Zhao et al.
gas molecule, Nxi was set to 1. μ xi (P, T) denotes the chemical potential
of an ideal gas molecule. The calculation formula of the chemical po­
tential under ideal conditions was given by [32]:
[ ( )3/2 ]
P h2
μxi (P, T) = kB Tln (5)
kB T 2πmg kB T
Where, T is the operating temperature (in Kelvin) of the gas sensors,
and P is the partial pressure of a certain gas molecule. kB is Boltzmann’s
constant, h is the Planck constant, and mg is the relative molecular mass
of each gas molecule.
Fig. 3 illustrates the relationship between the competitive adsorption
of the mixed gas and temperature. The ZnFe2O4 (111) surface exhibits
high selectivity for NH3, while demonstrating low selectivity for NO and
CO gas molecules. H2O gas molecule, as a background gas, significantly
influences the adsorption selectivity. On the other hand, N2 and O2,
despite having a large volume fraction, exhibit weak selectivity and have
minimal impact on adsorption. Therefore, it is necessary to control the
humidity of the detection environment or employ surface hydrophobic
treatment to reduce the influence of H2O. Within the temperature range
of 300 K to 700 K, the ZnFe2O4 (111) surface shows the highest selec­
tivity for NH3 (Fig. 3 (a) and (b)). In mixed gas without NH3, reducing
the partial pressure of H2O leads to high selectivity for H2S and NO2
(Fig. 3 (c) and (d)), with H2S being easier to capture. Importantly, in the
absence of NH3, the adsorption amount of the gas decreases with
Fig. 3. The occupation function values of gas molecules adsorbed on the ZnFe2O4 (111) surface at N2 partial pressure of 78%, O2 partial pressure of 21%, and the
relative partial pressure of these toxic gases is 100 ppm (a) H2O partial pressure of 2000 ppm (lower humidity), NH3 existed; (b) H2O partial pressure of 5000 ppm
(higher humidity), NH3 existed; (c) H2O partial pressure of 2000 ppm, NH3 inexistent; (d) H2O partial pressure of 5000 ppm, NH3 inexistent.
4
Colloid and Interface Science Communications 60 (2024) 100784
increasing temperature, and the highest selectivity for H2S and NO2 at
300 K.
3.3. Thermodynamic analysis of adsorption behavior
Regarding the effect of temperature on the adsorption, the adsorp­
tion free energy was calculated. The Gibbs free energy of an isolated gas
molecule and adsorption system can be obtained as [33,34]:
Ggas = Egas + EZPE + nRT − TS (6)
Gsub = Esub + EZPE + Ecv − TS (7)
Where, Ggas and Gsub are the Gibbs free energy of the isolated gas
molecule, and the ZnFe2O4 (111) surface after gases adsorption. Egas ,
Esub , EZPE and Ecv are the calculated energy of gases molecule, the total
energy of each gas molecule adsorbed on the ZnFe2O4 (111) surface,
zero-point energy (ZPE), and capacity correction. R and S denote the
ideal gas constant (8.31 J/(mol⋅K)) and entropy of the adsorption sys­
tems. The adsorption free energy is obtained as [33]:
ΔGad = Ggas/ZnFe2 O4 (111) − GZnFe2 O4 (111) − Ggas (8)
Where, Ggas/ZnFe2 O4 (111) , GZnFe2 O4 (111) and Ggas are the Gibbs free energy
of the ZnFe2O4 (111) surface after adsorption, before adsorption and
isolated gas molecule. Then, if ΔGad is more negative, the adsorption
system is more stable. It should be noted that only the partial Hessian
R. Zhao et al.
matrix of adsorbed each gas molecule is calculated to obtain the vibra­
tion frequency in order to improve computing efficiency.
The relationship between the adsorption free energy and tempera­
ture is shown in Fig. 4. It can be observed that as the temperature in­
creases from 300 K to 700 K, the adsorption free energy decreases
gradually. If the adsorption free energy is <0, indicating the adsorption
process is spontaneous. From Fig. 4, it is evident that the NH3 adsorption
system has the most negative adsorption free energy, indicating its
higher stability. On the other hand, the CO adsorption system consis­
tently displays a positive adsorption free energy, implying its lack of
spontaneous adsorption. Additionally, it can be inferred that NH3
adsorption is characterized by higher difficulty in desorption. The
intersection points of the adsorption free energy with 0 eV for the SO2,
H2O, NO2, H2S, and NH3 adsorption systems are approximately at 380 K,
410 K, 440 K, 480 K, and 680 K, respectively.
When the operating temperature surpasses the aforementioned
critical threshold, instability arises in the adsorption systems, resulting
in the desorption of gas molecules from the ZnFe2O4 (111) surface.
Therefore, it is imperative to ensure that the operating temperature of
ZnFe2O4 (111) gas sensors remains below the threshold temperature at
which the adsorption process occurs spontaneously. Combined with the
results of selective adsorption and adsorption free energy, the optimal
working temperature of the ZnFe2O4 (111) gas sensors for detecting
NH3, H2S and NO2 is 650 K, 450 K and 400 K, respectively.
3.4. Analysis of electronic characteristics
According to the results obtained from the analysis of competitive
adsorption and adsorption free energy, it can be concluded that the
ZnFe2O4 (111) surface exhibits a weak adsorption behavior towards NO,
CO, N2, and O2 gas molecules. Besides, the charge transfer in the SO2
adsorption system is minimal. Therefore, further investigation was
carried out to analyze the electronic properties of the adsorption systems
of NO2, NH3, H2S, and H2O. Various factors including QT, CDD, and DOS
were taken into account in order to gain a comprehensive understanding
of the adsorption behavior and micro-sensing electronic features of gas
molecules on the ZnFe2O4 (111) surface. For the NO2 adsorption system,
it was observed that the gas molecules gained a charge of 0.20 e (listed in
Table 1) from the adsorption surface. However, when H2S, NH3, and
H2O adsorbed, the gas molecules lost charges of 0.20 e, 0.14 e, and 0.19
e, respectively. The CDD and 2D charge density maps of the four
adsorption systems are presented in Fig. 5. The CDD on the left side is
used for qualitative analysis of the charge density, while the 2D charge
density map on the right side illustrates the direction of charge transfer
and the density of transferred charges. Positive electron density
Fig. 4. The adsorption free energy of different adsorption systems varies with
temperature.
5
Colloid and Interface Science Communications 60 (2024) 100784
indicates that the charge is transferred from the ZnFe2O4 (111) surface
to gas molecules.
In the case of the NO2/ZnFe2O4 (111) adsorption system (Fig. 5 (a)),
the charge transfer occurs from the ZnFe2O4 (111) surface to NO2
molecule. This is indicated by the presence of positive charge density
near NO2 molecule. The 2D charge density map further confirms this
charge accumulation near NO2 molecule. On the contrary, in the
adsorption systems of H2S, NH3, and H2O (Fig. 5 (b) ~ (d)), these gas
molecules act as charge donors. This is clearly indicated by the presence
of positive charge density at the position of gas molecules in the 2D
charge density maps. This analysis aligns with the findings of the charge
transfer quantity, which demonstrates strong chemical interactions be­
tween these gas molecules with the ZnFe2O4 (111) surface. These ana­
lyses provide valuable insights into the charge transfer mechanisms and
the interactions between gas molecules and the ZnFe2O4 (111) surface.
To further investigate the chemical interactions between adsorbed
gas molecules and the ZnFe2O4 (111) surface, the total density of states
(TDOS) before and after adsorption, as well as the partial density of
states (PDOS) of these gas molecules after adsorption were calculated, as
shown in Fig. 6. In the TDOS section, the black line represents the TDOS
of the ZnFe2O4 (111) surface before adsorption, and the red curve de­
notes the TDOS of the adsorption system after adsorption. The PDOS of
the adsorbed gas molecules and active sites Zn atoms are shown in the
PDOS section.
After NO2 gas molecules adsorbed, the TDOS of the NO2/ZnFe2O4
(111) adsorption system exhibits notable changes. In Fig. 6 (a), there is a
significant increase in TDOS at − 0.5 eV, − 2.5 eV, and − 6 eV, primarily
due to the overlap of the NO2 molecular orbitals O 2p and N 2p. Addi­
tionally, a new peak emerges at − 10 eV, mainly resulting from the
overlap of the NO2 molecular orbitals O 2 s, O 2p, and N 2 s. The overlap
between the adsorbed NO2 gas molecular orbitals and the ZnFe2O4 (111)
surface atomic orbitals Zn 3d near − 6 eV suggests a strong chemical
interaction between the adsorbed NO2 gas molecules and the substrate.
For the H2S adsorption system, the TDOS displays more pronounced
changes, with a new state appearing near − 14.5 eV. Furthermore, the
H2S molecular orbitals overlap with the Zn atomic orbitals near − 6 eV,
indicating a strong chemical interaction between the ZnFe2O4 (111)
surface and the adsorbed H2S.
Upon the adsorption of NH3 molecules on the ZnFe2O4 (111) surface,
the TDOS of the system undergoes significant changes, with a new state
appearing near − 8 eV. This new state is mainly formed by the overlap of
the NH3 molecular orbitals H 1 s and N 2p (Fig. 6 (c)). The ZnFe2O4
(111) surface exhibits a strong chemical interaction with the adsorbed
NH3. The ZnFe2O4 (111) surface demonstrates a strong chemical
adsorption effect on H2O molecules, as evidenced by the overlap of the
surface Zn atomic orbitals with the adsorbed H2O molecular orbitals. A
new state composed of H 1 s and O 2p emerges near − 9.5 eV (Fig. 6 (d)).
Through DOS analysis, it can be observed that the ZnFe2O4 (111) surface
exhibits a strong chemical adsorption effect on the adsorbed NO2, H2S,
NH3, and H2O gas molecules.
3.5. Analysis of gas sensing characteristics
ZnFe2O4 is an N-type metal oxide semiconductor, with electrons as
the majority charge carriers [13,21]. The gas sensing properties of
ZnFe2O4 are closely related to adsorption energy and charge transfer. In
an environment without target harmful gases, the Zn3C atoms on the
ZnFe2O4 (111) surface quickly adsorb O2 molecules from environment
due to their strong reducibility and lack of coordinated oxygen. This
leads to the formation of an electron-depleted layer (shown in Fig. 7 (a))
on the ZnFe2O4 (111) surface [21]. Consequently, the ZnFe2O4 (111) gas
sensors exhibit high resistance in environment without the target gas
molecules.
As illustrated in Fig. 7(b), the adsorption of NH3, H2S, and H2O on
the ZnFe2O4 (111) surface has a tendency to reduce the thickness of
electron depletion layer and decrease the resistance. Following the
R. Zhao et al.
Fig. 5. CDD and 2D electron density of gas molecules after adsorption on the ZnFe2O4 (111) surface (a) NO2; (b) H2S; (c) NH3; (d) H2O (The blue region denotes
electron accumulation while the yellow region represents electron depletion. The red arrows point to the direction of charge transfer. The vacuum lay is 15 Å, and the
charge transfer of adsorbed gas molecules is distributed form 8 Å to 15 Å). (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
adsorption process, electrons transfer from NH3, H2S, and H2O gas
molecules to the ZnFe2O4 (111) surface, inducing an increased number
of free electrons on the surface. This thinner electron depletion layer
indicates a smaller value for the sensor’s resistance. Notably, NH3 ex­
hibits the strongest selective adsorption, causing the resistance to
decrease at a faster rate compared to the other gases. While NO2 mol­
ecules adsorbed, electrons transfer from the ZnFe2O4 (111) surface to
NO2 molecules, leading to a decrease in the majority charge carrier
electrons and a thicker electron depletion layer (shown in Fig. 7(c)),
resulting in an increase in resistance. It is worth noting that the inclusion
of H2O molecules significantly affects the adsorption selectivity of other
gas molecules. The presence of H2O molecules hinders the adsorption
process of H2S and NO2 molecules, hence necessitating the consideration
of humidity’s influence. In cases where the working temperature is
excessively high, gas molecules may encounter difficulties in adsorbing
on the ZnFe2O4 (111) surface, consequently leading to an increase in
resistance.
4. Conclusions
In this work, the selective adsorption and sensing properties of toxic
gas and background gas molecules on the ZnFe2O4 (111) surface were
explored. The results suggest that the ZnFe2O4 (111) surface holds a
significant potential for detecting toxic gases. Through a systematic
analysis, the following conclusions have been drawn:
(1) NH3, H2S, H2O, and NO2 gas molecules exhibit a high adsorption
energy and significant interaction with the ZnFe2O4 (111)
surface.
(2) NH3 demonstrates the highest competitive adsorption. If the
interference of NH3 is eliminated and the humidity of the test gas
is controlled, the selective adsorption of the ZnFe2O4 (111) sur­
face for H2S and NO2 is relatively high at 300 K.
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Colloid and Interface Science Communications 60 (2024) 100784
(3) The charge transfer in these four adsorption systems is signifi­
cant. The charge transfer direction of the NO2 adsorption system
is from the ZnFe2O4 (111) surface to NO2 molecules, leading to an
increase in resistance. However, in the H2S, NH3, and H2O
adsorption systems, these gas molecules act as electron donors,
resulting in a decrease in resistance.
(4) The ZnFe2O4 (111) surface exhibits a strong chemical adsorption
effect on adsorbed NO2, H2S, NH3, and H2O molecules, demon­
strated by the overlap of Zn atomic orbital with these adsorbed
gas molecules orbitals.
In summary, this theoretical study offers valuable insights into the
detection of toxic gases. It provides guidance for the experimental
implementation of ZnFe2O4 (111) as promising gas sensing materials in
diverse gas sensors technologies. In order to enhance the selective
adsorption of ZnFe2O4 (111) gas sensors towards diverse gases, our
forthcoming endeavors will encompass additional theoretical and
experimental investigations, including exploring composite doping
approaches.
CRediT authorship contribution statement
Renchu Zhao: Writing – original draft, Visualization, Data curation.
Dachang Chen: Writing – review & editing, Writing – original draft,
Supervision, Investigation, Funding acquisition, Formal analysis. Jie Li:
Investigation, Formal analysis. Qing Miao: Methodology, Investigation.
Ke Liu: Visualization, Data curation. Beibei Xiao: Software, Resources.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
R. Zhao et al.
Fig. 6. TDOS of ZnFe2O4(111) surface before and after gases molecule adsorption, PDOS of adsorbed gas molecule (a) NO2; (b) H2S; (c) NH3; (d) H2O.
Fig. 7. Changes in the electron depletion layer due to the adsorption of
different gas molecules (a) O2; (b) NH3, H2S, and H2O; (c) NO2 (The red arrows
point to the direction of charge transfer). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of
this article.)
7
Colloid and Interface Science Communications 60 (2024) 100784
Data availability
Data will be made available on request.
Acknowledgements
This research was supported by the Natural Science Foundation of
Hubei Province (Grant No. 2022CFB941), the Research and Innovation
Initiatives of WHPU (Grant No. 2022Y25), the Research Funding of
WHPU (Grant No. 2022RZ009) and the 2022 Special Subsidy Funding of
WHPU (Grant No. 03220153).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.colcom.2024.100784.
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