Sensors & Actuators: B.

Chemical 325 (2020) 128783

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Sensors and Actuators: B. Chemical

journal homepage: www.elsevier.com/locate/snb

MOF-derived ZnFe2O4/(Fe-ZnO) nanocomposites with enhanced acetone

sensing performance
Ensi Cao a, b, *, Zhaoqing Guo a, Guoqing Song a, Yongjia Zhang a, Wentao Hao a, Li Sun a,
Zhongquan Nie b
a
College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, PR China
b
Key Lab of Advanced Transducers and Intelligent Control System, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, PR China

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

Keywords: To further improve the acetone sensing performance of MOF-derived ZnO nanoparticles, the doping of Fe into the
ZnO ZnO lattice and the heterostructure formation with ZnFe2O4 nanoparticles were simultaneously achieved by a
Zn solution-based method via the hydrolyzation of Zn-based MOF-5 in Fe(NO3)3 aqueous solution. The obtained
Fe2O4
ZnFe2O4/(Fe-ZnO) nanocomposites (the mole ratio of Fe/Zn = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) were
MOF
characterized and confirmed by XRD, TEM, SAED, Element mapping, SEM, XPS and BET. Compared with the
Nanocomposite
Acetone sensing pristine ZnO nanoparticles, better acetone sensing characteristics in terms of gas response, sensitivity, stability,
XPS reproducibility and selectivity were achieved by the ZnFe2O4/(Fe-ZnO) nanocomposites at lower prime working
temperatures, among which the nanocomposites with Fe/Zn = 0.15 exhibited the best comprehensive perfor­
mance due to its largest BET surface area, abundance of adsorption sites for oxygen and acetone molecules, as
well as the high and wide potential barrier at the interfaces.

1. Introduction
Acetone, a kind of extensively used hazardous chemicals in various
industrial processes, can give rise to central nervous system anesthesia,
skin and eyes irritation, and nausea. Besides, the acetone in human
breath exhaust can be utilized as a critical biomarker for the noninvasive
diagnosis of diabetes in early stage. Consequently, it is of significant
importance to make high-performance acetone sensors for the sake of
environment and human health [1,2].
Zinc oxide (ZnO) has been extensively studied as acetone sensing or
modifying material due to its high chemical stability, electron mobility,
and structure tunability [3–6]. However, the high working temperature,
low sensitivity, and poor selectivity still need to be improved to satisfy
the requirement of practical application. Metal oxide frameworks
(MOFs), consisted of metal cations or metal cation aggregates linked by
organic ligand molecules, are promising materials for application in the
sensing field due to the high porosity, specific surface area, and tena­
bility of morphology [7]. However, the high electrical resistance hinders
MOFs from direct application as electrical sensing material. While the
thermal annealing of MOF precursors could result in metal oxides
semiconductors (MOSs) preserving the morphology and porous
structure of MOFs, and the high specific surface area makes the
MOF-derived MOSs exhibit better gas sensing performance. The ZnO
nanocages prepared by the thermal decomposition of Zn-based MOF-5
showed good sensitivity and selectivity towards acetone owing to the
more exposed active sites and large specific surface area, which
benefited the diffusion and reaction of acetone molecules on the surface
[8]. To further improve the acetone sensing performance of
MOF-derived ZnO nanomaterials, the introduction of noble metal Au
was frequently utilized due to its catalytic activity and chemical sensi­
tization effect [9,10]. Additionally, the heterostructure of ZnFe2O4/ZnO
was widely studied owing to the electrical sensitization effect of
ZnFe2O4, which can be beneficial for carrier transfer and increase in
depletion layer width [2,11–13]. In these studies, the heterostructure
was reported to be achieved by the thermal annealing of MOFs, such as
Prussian Blue analogue of Zn3[Fe(CN)6]2⋅xH2O [2] and Fe(III)-doped
MOF-5 [11], or by immersing the as-prepared ZnO in Fe-contained
aqueous solution, such as FeSO4 [12] and Fe(NO3)3 [13].
Herein, the synergistic effect of doping and heterostructure forma­
tion on the acetone sensing performance of MOF-derived ZnO nano­
particles was studied by comparing the acetone sensing characteristics
of pristine ZnO nanoparticles and ZnFe2O4/(Fe-ZnO) nanocomposites.

* Corresponding author at: College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, PR China.
E-mail address: caoensi@163.com (E. Cao).

https://doi.org/10.1016/j.snb.2020.128783
Received 29 February 2020; Received in revised form 4 June 2020; Accepted 18 August 2020
Available online 21 August 2020
0925-4005/© 2020 Elsevier B.V. All rights reserved.
E. Cao et al.
Fig. 1. XRD patterns of (a): as-prepared MOF-5 and (b): MOF-5 after immersion in Fe(NO3)3 aqueous solution with x = 0.15.
The pristine ZnO nanoparticles were prepared by the thermal annealing
of Zn-based MOF-5 synthesized by a conventional solvothermal method,
while a new route to prepare ZnFe2O4/(Fe-ZnO) nanocomposites with
different mole ratios of Fe/Zn was provided by immersing Zn-based
MOF-5 in Fe(NO3)3 aqueous solution before annealing treatment. The
ZnFe2O4/(Fe-ZnO) nanocomposites were confirmed and characterized
by XRD, TEM, SAED, Element mapping, SEM, XPS and BET, and the
origin for the best acetone sensing performance of ZnFe2O4/(Fe-ZnO)
nanocomposite with Fe/Zn = 0.15 was analyzed from the perspectives of
reception and conduction mechanisms.
2. Experimental details
2.1. Preparation of sensing materials
The precursor of Zn-based MOF-5 powders was synthesized by a
solvothermal method. Specifically, 10 mmol Zn(NO3)2⋅6H2O and
5 mmol 1,4-benzenedicarboxylic acid (H2BDC) were added into the
mixed solvent of 50 mL dimethylformamide (DMF) and 10 mL methanol.
After ultrasonic treatment for 15 min., the obtained mixture in a 100 mL
autoclave was kept in an oven at 150 ◦ C for 12 h. Upon centrifugation,
the obtained precipitate was washed by DMF for three times and dried at
160 ◦ C for 12 h to get the MOF-5 powders. The final products of pristine
ZnO nanoparticles were prepared by heating the as-prepared MOF-5
powders in air at 500 ◦ C for 2 h. Setting the mole ratio of Fe/Zn as x
(x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30), MOF-5 powders were
immersed in aqueous solution of Fe(NO3)3⋅9H2O containing the
required amount of Fe. The mixed solution was under constant stirring
at 80 ◦ C in a water bath until it was totally dried. The obtained powers
were finely ground and calcined in air at 500 ◦ C for 2 h to get a series of
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Sensors and Actuators: B. Chemical 325 (2020) 128783
ZnFe2O4/(Fe-ZnO) nanocomposites.
2.2. Characterization of sensing materials
The crystalline structure of as-obtained pristine ZnO nanoparticles
and ZnFe2O4/(Fe-ZnO) nanocomposites was measured by X-ray
diffractometer (D/max 2500, Rigaku Corporation, Japan) using Cu Kα
radiation. The morphology was examined by field emission scanning
electron microscope (FE-SEM) (JSM-6700 F, JEOL Ltd, Japan). The
element mapping was performed by Transmission Electron Microscope
(TEM) (JEM-2010, JEOL Ltd, Japan). The surface composition was
checked by X-ray Photoelectron Spectrometer (XPS) with mono­
chromated Al Kα radiation (Escalab 250, Thermo Electron Corporation,
USA). The BET surface area was obtained by Surface Area and Porosity
Analyzer (ASAP 2460, Micromeritics Instruments Corporation, USA).
2.3. Fabrication and measurements of sensors
Indirectly heated gas sensors were fabricated by coating the pristine
ZnO nanoparticles and ZnFe2O4/(Fe-ZnO) nanocomposites on ceramic
tubes, followed by calcination in air at 200 ◦ C for 2 h and aging at 200 ◦ C
for 48 h to achieve stable sensor configuration. The details about the
fabrication process and ceramic tube can be found in our previous work
[14]. The acetone sensing measurement of the sensors was performed in
an atmosphere with the relative humidity of 15 % by an Intelligent Gas
Sensing Analysis System (CGS-8, Beijing Elite Tech Co., Ltd. China). The
gas response of the sensors was defined as the ratio of resistance in dry
air (Ra) over that in target gas (Rg), and the response and recovery time
were defined as the time taken to achieve 90 % of the total resistance
variation in the case of adsorption and desorption, respectively.
E. Cao et al. Sensors and Actuators: B. Chemical 325 (2020) 128783

Fig. 2. SEM images of (a): as-prepared MOF-5 powder; (b): typical MOF-5 cube, (c) and (d): typical ZnO microspheres and corresponding local magnified image; (e)
and (f): MOF-5 powder after immersion in Fe(NO3)3 aqueous solution with x = 0.15 and corresponding local magnified image.

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Fig. 3. XRD patterns and TEM images of (a) and (c): ZnO nanoparticles; (b) and (d): ZnFe2O4/(Fe-ZnO) nanocomposite with x = 0.15.
3. Results and discussion
3.1. Characterization of sensing materials
Fig. 1a and 1b show the XRD patterns of the as-prepared MOF-5 and
that after immersion in Fe(NO3)3 aqueous solution with x = 0.15,
respectively. The as-prepared MOF-5 showed the main phase of MOF-5
and the trace phase of hexaganol ZnO (PDF#89− 1397). The diffraction
peaks at around 7.1◦ , 9.8◦ , 13.9◦ , and 15.6◦ correspond to the charac­
teristic diffractions of (200), (220), (400) and (420) from MOF-5
[15–17], while the peaks at 31.7◦ and 36.4◦ are assigned to the
featured (100) and (101) peaks of hexaganol ZnO [11–13]. The well
resolved peaks imply the high crystallinity of MOF-5, and the stronger
diffractions of (400) and (200) than other diffractions indicate the
preferred orientation along (100) for the microcrystalline MOF-5. As for
the sample after immersion in Fe(NO3)3 aqueous solution, the mixed
phases of MIL-53(Fe) [18–20] and Zinc hydroxide nitrate hydrate (Zn
(OH)(NO3)(H2O)) appear instead of MOF-5 and ZnO. This can be
explained by the decomposition of MOF-5 into Zinc salt and H2BDC in
aqueous solution, the concomitant reconstruction of MIL-53(Fe) by Fe3+
ions and H2BDC, and the transformation of ZnO into Zinc salt in Fe
(NO3)3 aqueous solution.
The surface morphology of the as-prepared MOF-5 powder and that
after immersion in Fe(NO3)3 aqueous solution with x = 0.15 was
checked by FE-SEM, and the results are displayed in Fig. 2. As seen from
Fig. 2a, the as-prepared MOF-5 powder is mainly composed of MOF-5
cubes, on the surface of which some ZnO microspheres grow. The
typical MOF-5 cube and ZnO microsphere are presented in Fig. 2b and
2c, respectively. The local magnified image of the ZnO microsphere in
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Sensors and Actuators: B. Chemical 325 (2020) 128783
Fig 0.2d indicates that the porous microsphere consists of pillars made of
ZnO nanoparticles. As for the sample after immersion in Fe(NO3)3
aqueous solution, it is composed of MIL-53(Fe) backbones covered by
the sheet bars of Zinc hydroxide nitrate hydrate, as revealed by Fig. 2e
and 2f.
After calcination at 500 ◦ C for 2 h, the as-prepared MOF-5 powder
turned into pristine ZnO nanoparticles and those after immersion in Fe
(NO3)3 aqueous solution became the ZnFe2O4/(Fe-ZnO) nano­
composites. Fig. 3 shows the XRD patterns and TEM images of the
pristine ZnO nanoparticles and the ZnFe2O4/(Fe-ZnO) nanocomposite
with x = 0.15. The phase of hexaganol ZnO (PDF#89− 1397) could be
observed in both samples. Based on the ZnO diffraction peaks, the lattice
parameters, unit cell volume, strain and average crystallite size were
calculated using the Scherrer formula. Compared with the pristine ZnO,
the unit cell volume of ZnO in the ZnFe2O4/(Fe-ZnO) nanocomposite
decreased from 47.80 Å3 to 47.75 Å3, the strain increased from 0.037 %
to 0.079 %, and the average crystallite size increased from 36.5 nm to
74.0 nm. These facts indicate that the smaller Fe ions might incorporate
into the ZnO lattice and occupy some Zn2+ sites, which in turn resulted
in the contraction of lattice and the increase of strain inside the ZnO
nanoparticles. Besides hexaganol ZnO, the nanocomposite showed the
independent phase of cubic ZnFe2O4 (PDF#74− 2397) [11–13]. As
typically indicated by the green hexagons in the TEM images, the ZnO
nanoparticles in both samples mainly existed in the shape of hexagons
which are in accordance with its crystalline structure. While the smaller
nanoparticles inside the red circles and those dispersed in-between the
ZnO nanoparticles are assigned to be the ZnFe2O4 nanoparticles. On the
basis of 100 particles in clear outlines, the mean particle sizes of ZnO in
the pristine ZnO nanoparticles and ZnFe2O4/(Fe-ZnO) nanocomposite
E. Cao et al. Sensors and Actuators: B. Chemical 325 (2020) 128783

Fig. 4. TEM (a) and corresponding SAED (b) images of the ZnFe2O4/(Fe-ZnO) nanocomposite with x = 0.15.

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Fig. 5. Element mapping and STEM images for the ZnFe2O4/(Fe-ZnO) nanocomposite with x = 0.15 (BF, Bright Field; HAADF, High Angle Annular Dark Field).

Fig. 6. Whole survey, Zn2p, O1s, and Fe2p core level XPS of the pristine ZnO nanoparticles and ZnFe2O4/(Fe-ZnO) nanocomposite with x = 0.15 (oct, octahedral; tet,
tetrahedral; sat, satellite).

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Fig. 7. SEM images of ZnO nanoparticles (a) and (b): in the microstructure of cube and corresponding local magnified image; (c) and (d): in the microstructure of
sphere and corresponding local magnified image; (e)-(j): ZnFe2O4/(Fe-ZnO) nanocomposites with x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30, respectively.

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Fig. 8. BET surface area (left) and average pore size (right) of ZnFe2O4/(Fe-
ZnO) nanocomposites with different x values.
and the mean particle size of ZnFe2O4 in the nanocomposite were esti­
mated to be 43.5 nm, 63.6 nm and 15.5 nm, respectively, which were
close to the average crystallite sizes of 36.5 nm, 74.0 nm and 18.5 nm
estimated by the XRD. The polycrystalline nature of the Fe-ZnO and
ZnFe2O4 nanoparticles was further verified by their characteristic
diffraction rings in the SAED image in Fig. 4.
Since the diffraction peaks of Fe2.93O4 and ZnFe2O4 are very close to
each other, it is difficult to distinguish merely from the XRD patterns.
Therefore, the element mapping in combination with the STEM in the
Bright Field (BF) and High Angle Annular Dark Field (HAADF) were
performed on the nanocomposite with x = 0.15, and the results were
displayed in Fig. 5. Apparently, Zn, Fe and O could be observed in the
yellow circle, which means that the inside particle should be ZnFe2O4
rather than Fe2.93O4. The particles with Fe atoms in the dense state
should be ZnFe2O4 as well, while the particles having dense Zn and O
atoms as well as sparsely distributed Fe atoms should be the Fe-doped
ZnO nanoparticles.
Fig. 6 shows the whole survey and elemental XPS in the core level of
the pristine ZnO nanoparticles and the ZnFe2O4/(Fe-ZnO) nano­
composite with x = 0.15, with the binding energy (BE) in all spectra
charge-shifted relative to the C–C bond at 284.8 eV. Except the carbon
from the unavoidable contamination, all peaks in the whole survey
spectra (Fig. 6a) can be assigned to the Zn and O core level peaks and
Auger peaks, confirming the purity of elements in both samples. In
Fig. 6b, the peaks at the BE of 1021.3 eV and 1044.4 eV in both samples
are assigned to the Zn2p3/2 and 2p1/2 spin-orbit components in ZnO,
respectively, while the peaks at the BE of 1021.9 eV and 1045.4 eV for
the ZnFe2O4/(Fe-ZnO) nanocomposite were ascribed to the Zn2p3/2 and
2p1/2 spin-orbit components in ZnFe2O4 [2,12]. In Fig. 6c, the peak at
the BE of 530.1 eV is assigned to the lattice oxygen (OL) in ZnO or
ZnFe2O4, while the peak around 531.6 eV is ascribed to the chemisorbed
oxygen species (OC) on the surface [10,21]. Because the Fe in ZnFe2O4 or
ZnO can result in the stronger Fe-O bond than Zn-O bond on the surface,
the BE of OC is increased to 531.7 eV in the composite. The Fe2p core
level XPS for the ZnFe2O4/(Fe-ZnO) nanocomposite is displayed in
Fig. 6d, which shows Fe in three different valence states [22]. The
normal Fe3+ and reduced Fe2+ species should originate from the Fe ions
in the ZnFe2O4 and ZnO lattices, while the metallic Fe atoms might be
sparsely located on the surface of ZnO nanoparticles. The Fe species in
the reduced state should be caused by the reducing carbide and nitride
emitted during the annealing process.
The surface morphology of the pristine ZnO and the ZnFe2O4/(Fe-
ZnO) nanocomposites with x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30
were displayed by the FE-SEM images in Fig. 7. As shown in Fig. 7a and
7c, the pristine ZnO nanoparticles preserved the microstructure of cube
and sphere as in the as-prepared MOF-5 powder before calcination.
While the local magnified images in Fig. 7b and 7d indicate that the cube
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Sensors and Actuators: B. Chemical 325 (2020) 128783
and sphere are in the porous structure and compose of ZnO nano­
particles in uniformly distributed size. Fig. 7e-7 j display the SEM images
of the ZnFe2O4/(Fe-ZnO) nanocomposites with x = 0.05, 0.10, 0.15,
0.20, 0.25 and 0.30, respectively, which all showed the porous structure
of nanoparticles. Inferred by the analyses above, the bigger particles in
these images should be ZnO nanoparticles, while the smaller ones should
be ZnFe2O4 nanoparticles. To further check the effect of Fe/Zn mole
ratios on the microstructure of nanocomposites, BET measurement was
performed, and the results of BET surface area and mean pore size for
each sample are depicted in Fig. 8. The pristine ZnO nanoparticles
possess the largest surface area and smallest pore size due to its pre­
served microstructure of MOF-5 cubes and ZnO spheres. As for the
ZnFe2O4/(Fe-ZnO) nanocomposites, with the increase of Fe/Zn mole
ratio, the BET surface area increases at first, reaches a maximum at
x = 0.15, then decreases again. Basically, a larger surface area corre­
sponds to a smaller mean pore size.
3.2. Acetone sensing performance and mechanism
Fig. 9 shows the acetone sensing characteristics of the pristine ZnO
nanoparticles and the ZnFe2O4/(Fe-ZnO) nanocomposite-based sensors.
The temperature dependence of resistance in Fig. 9a shows that all the
nanocomposites showed higher resistance than the pristine ZnO nano­
particles due to the existence of ZnFe2O4 insulating phase. For the same
reason, higher ratios of Fe/Zn in the nanocomposites resulted in higher
resistance. From the operating temperature dependence of the gas
response to 100 ppm acetone in Fig. 9b, the prime working temperature
(TP) where the gas response reaches its maximum was determined to be
270 ◦ C for the pristine ZnO sensor, while the TP shifted to lower tem­
perature with the increase of x value for the ZnFe2O4/(Fe-ZnO) nano­
composites. The highest gas response of 30.8, which was almost four
times the value of 8.2 for the ZnO sensor at 270 ◦ C, was achieved by the
nanocomposite with x = 0.15 at the TP of 190 ◦ C. The variation in gas
response over the variation in concentration of target gas reflects the
sensitivity of the sensor. It can be seen from Fig. 9c that at the TP of each
sensor the nanocomposite with x = 0.15 exhibited the highest sensitivity
among all sensors in the range of 10− 200 ppm. For practical application,
the selectivity of the sensors must be considered. Fig. 9d displays the gas
responses to 100 ppm different target gases at the TP of each sensor. The
ratio of the gas response to acetone over the response to EG, DMF,
ammonia water, N-hexane or carbon dioxide was much higher for the
ZnFe2O4/(Fe-ZnO) sensors than that for the pristine ZnO sensor, which
means that the ZnFe2O4/(Fe-ZnO) nanocomposites showed higher
selectivity towards acetone than that of ZnO nanoparticles. The reason
for the enhanced selectivity towards target gas is still unclear now,
which is supposed to be associated with some intrinsic properties of
target gases, such as the reaction activity in terms of bond energy [23,
24], the dipole moment in the molecular structure [25], the molecular
size and molecular weight [26]. Besides, the porous structure of the
sensing matrix in terms of pore size is reported to determine the diffu­
sion type of target gas by comparing the mean free path of target gas and
mean pore size, which will also contribute to the selectivity of sensing
material [27].
For the pristine ZnO and the ZnFe2O4/(Fe-ZnO) nanocomposite with
x = 0.15, Fig. 9e depicts the dynamic responses of resistance to 100 ppm
acetone at each TP in three consecutive measurements. Both sensors
showed good recovery, stability, and reproducibility, and the ZnFe2O4/
(Fe-ZnO) sensor displayed even more stable resistance than the ZnO
sensor after gas was taken out. The mean response time for the ZnFe2O4/
(Fe-ZnO) sensor was calculated to be 4.7 s which was longer than the
3.3 s for the ZnO sensor, while the mean recovery time of 10.3 s was
smaller than the 11.0 s for the ZnO sensor. The above sensing mea­
surements were all performed in an atmosphere of 15 % relative hu­
midity. To study the effect of relative humidity (RH) on the sensing
performance, the RH dependence of gas responses to 100 ppm acetone
for the pristine ZnO and the nanocomposite with x = 0.15 was examined
E. Cao et al. Sensors and Actuators: B. Chemical 325 (2020) 128783

Fig. 9. For the ZnFe2O4/(Fe-ZnO) nanocomposites-based sensors with x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30, (a): temperature dependence of resistance from
170 to 290 ◦ C; (b): temperature dependence of gas response to 100 ppm acetone from 170 to 290 ◦ C; (c): gas responses to different concentration of acetone at each
prime working temperature; (d): gas responses to 100 ppm different target gases at each prime working temperature. (e): dynamic responses of resistance to 100 ppm
acetone at each prime working temperature in three consecutive measurements for x = 0 and 0.15; (f): relative humidity dependence of gas responses to 100 ppm
acetone at 190 ◦ C for x = 0 and 0.15.

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Table 1
Lattice parameters, unit cell volume (V), average crystallite size (DC), strain (σ), mean particle size (DP) of ZnO in the pristine ZnO nanopartilces (ZnOP) and ZnFe2O4/
(Fe-ZnO) nanocomposite (ZnOC) with x = 0.15, and these parameters of ZnFe2O4 in the nanocomposite.
Phase a (Å) b (Å) c (Å) V (Å3) DC (nm) σ (%) DP (nm)

ZnOP 3.2530 3.2530 5.2127 47.77 36.5 ± 0.6 0.037 43.5

ZnOC 3.2529 3.2529 5.2103 47.75 74.0 ± 5.5 0.079 63.6
ZnFe2O4 8.4716 8.4716 8.4716 607.99 18.5 ± 1.3 0 15.5

Table 2
Comparison between the acetone sensing performance of ZnO-based composites reported in literature, including prime working temperature (TP), gas response, and
response/recovery time (TRes/Trec).
Sensing material Preparation method Structure TP Response TRes/Trec Ref.

CeO2/ZnO Solvothermal Dual porous composite 320℃ 16.0− 5 ppm / [29]

α-Fe2O3/ZnO Hydrothermal and sol-gel Nanotubes 369℃ 32.0− 100 ppm / [30]
α-Fe2O3/ZnO Hydrothermal Core-shell nanospindles 280℃ 12.0− 100 ppm / [31]
NiO/ZnO Solution-based Flower-like 300℃ 23.5− 100 ppm / [32]
NiO/ZnO Chemical bath deposition Flower-like 330℃ 13.5− 100 ppm* / [33]
NiO/ZnO Solvothermal Yolk-double-shelled microspheres 260℃ 7.5− 200 ppm 8s/13 s [34]
ZnCo2O4/ZnO Solution-based ZnCo2O4 nanodots on ZnO nanorods 240℃ 15.3− 10ppm 7.7 s/10.3 s [35]
SmFeO3/ZnO Solution-based Nanocomposite 350℃ 45− 10ppm 10− 15 s /250− 400 s [36]
ZnFe2O4/ZnO Prussian Blue analogue derived Hollow microspheres 140℃ 14.0− 100 ppm 5.2 s/12.8s [2]
ZnFe2O4/ZnO Thermal annealing of Fe(III)MOF-5 Hollow nanocages 290℃ 25.8− 100 ppm 8s/32 s [11]
ZnFe2O4/ZnO Solution-based ZnFe2O4 nanoparticles on ZnO microflowers 250℃ 8.3− 50ppm 2 s/25s [13]
ZnFe2O4/ZnO Solvothermal Core-shell hollow microspheres 280℃ 18.0− 80ppm* 8s/30 s [37]
ZnFe2O4/ZnO Hydrolyzation of MOF-5 Nanocomposite 190 ◦ C 30.8− 100 ppm 4.7 s/10.3 s This work
*
Inferred from data in graphic.

at the same temperature of 190 ◦ C to minimize the effect of temperature

on the adsorbing state of water molecules on both samples. The results in
Fig. 9f indicate that the RH had a considerable negative effect on the gas
response of both samples owing to the competing relationship between
the water and oxygen molecules on the surface adsorbing sites as well as
the reverse contribution to the width of electron depletion layer [28].
Table 1
The acetone sensing characteristics of ZnO-based composites re­
ported in literature are compared in Table 2. Compared with the CeO2/
ZnO, α-Fe2O3/ZnO, NiO/ZnO, ZnCo2O4/ZnO, SmFeO3/ZnO composites
[29–36], our ZnFe2O4/ZnO nanocomposite exhibited much lower TP
and faster dynamic response with relatively high gas response. As for
other ZnFe2O4/ZnO composites reported in literature [2,11,13,37], our
sample displayed the highest gas response with comparatively lower TP
and faster dynamic response. Therefore, the ZnFe2O4/ZnO nano­
composite in our work, as sensing material, is featured by high response,
fast response/recovery speed at low prime working temperature with
good reliability.
When the n-type ZnFe2O4/(Fe-ZnO) nanocomposite is exposed in air,
the oxygen in air will adsorb on the surface of ZnFe2O4 and Fe-ZnO
nanoparticles and undergo the following reactions as temperature rises.
O2(gas) ↔ O2(ads)
O2(ads) + e− ↔ O−2(ads)
C3 H6 O + 8On−ads →3CO2 + 3H2 O + 8ne− (5)
The improved acetone sensing performance of the ZnFe2O4/(Fe-
ZnO) nanocomposite can be analyzed by the reception and transduction
mechanisms. Firstly, the mismatched lattice caused by the incorporation
of Fe into the ZnO lattice, the interfaces between ZnFe2O4 and Fe-ZnO
nanoparticles, and the grain boundaries in-between ZnFe2O4 nano­
particles are all high energy sites favoring the adsorption of oxygen and
acetone. Therefore, the ZnFe2O4/(Fe-ZnO) nanocomposite with x = 0.15
which has the largest BET surface area exhibited the highest gas
response due to its abundance of adsorption sites and higher surface
oxygen coverage. Secondly, ZnFe2O4 is an n-type semiconductor with
higher Fermi level than that of ZnO, thus electrons would flow from
ZnFe2O4 to ZnO across the interface of ZnFe2O4/(Fe-ZnO) hetero­
structure. This charge redistribution results in electron accumulation in
the ZnO and electron depletion in the ZnFe2O4. More electrons on the
ZnO surface would benefit the oxygen adsorption from air and result in
wider depletion layer. Given the small particle size of 15.5 nm, the
remained electrons in the ZnFe2O4 nanoparticles could be completely
depleted by the adsorbed oxygen [39]. The wider depletion layer at the
ZnO surface, the completely depleted ZnFe2O4, as well as the higher and
wider potential barrier at the interfaces give rise to a larger measurable
(1)
variation in resistance when the adsorbed oxygen species are removed
(2) by surface interactions with acetone.

O−2(ads) + e− ↔ 2O−(ads) (3) 4. Conclusion

O−(ads) + e− ↔ O2−(ads)
As illustrated in Fig. 10a, a depletion layer would be formed on the
surface of ZnFe2O4 and Fe-ZnO nanoparticles due to the oxygen
adsorption. Given the weak nature of direct interaction between the
acetone and surface, the conductivity is considered to be mainly
controlled by the indirect chemical reaction between adsorbed oxygen
species (On−
ads ) and introduced acetone as Eq. (5) [38], which will lead to
the decrease in the width of electron depletion layer for the ZnFe2O4 and
Fe-ZnO nanoparticles, as illustrated in Fig. 10b.
(4) A series of ZnFe2O4/(Fe-ZnO) nanocomposites (the mole ratio of Fe/
Zn = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) was prepared by a
solution-based method via the hydrolyzation of Zn-based MOF-5 in Fe
(NO3)3 aqueous solution. XRD, TEM, SAED, Element mapping and XPS
confirmed the composition of cubic ZnFe2O4 and Fe-doped hexagonal
ZnO in the nanocomposites. Compared with the MOF-5-derived pristine
ZnO nanoparticles, the ZnFe2O4/(Fe-ZnO) nanocomposites, especially
the one with Fe/La = 0.15, exhibited enhanced gas response, higher
sensitivity, improved stability and reproducibility, faster recovery, and
better selectivity to acetone at lower prime working temperature. From
the perspectives of reception and transduction mechanisms, the

10
E. Cao et al. Sensors and Actuators: B. Chemical 325 (2020) 128783

Fig. 10. Schematic diagram of structure and band for the ZnFe2O4/(Fe-ZnO) nanocomposite-based sensor in air (a) and in acetone (b).

11
E. Cao et al.
enhanced acetone sensing performance should be contributed by the
synergistic effect of Fe-doping and heterostructure formation on the
material’s porous structure, adsorption sites, and modulation of poten­
tial barrier at the interfaces. Looking forward, the preparation of
nanocomposite through the hydrolyzation of MOF material in transition
metal aqueous solution may be a facile and effective way in improving
the gas sensing performance of MOF-derived nanoparticles by the syn­
ergistic effect of doping and heterostructure formation, while more work
needs to be done to weaken the strong dependence of gas response on
the surrounding humidity for practical application.
CRediT authorship contribution statement
Ensi Cao: Conceptualization, Methodology, Writing - original draft,
Writing - review & editing. Zhaoqing Guo: Investigation. Guoqing
Song: Validation. Yongjia Zhang: Data curation. Wentao Hao: Re­
sources. Li Sun: Project administration. Zhongquan Nie: Formal
analysis.
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.
Acknowledgments
This work was supported by the Natural Science Foundation of
Shanxi Province (201901D111117 and 201901D111126), and National
Natural Science Foundation of China (11604236 and 11974258).
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