Materials Science in Semiconductor Processing xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Science in Semiconductor Processing

journal homepage: http://www.elsevier.com/locate/mssp

Cu-doped Fe2O3 porous spindles derived from metal-organic frameworks

with enhanced sensitivity to triethylamine
Huijun Gao a, Yuzhen Ma b, Peng Song a, *, Zhongxi Yang a, Qi Wang a, **
a
School of Material Science and Engineering, University of Jinan, Jinan, 250022, China
b
Shandong Institute of Commerce & Technology, Jinan, 250101, China

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

Keywords: The introduction of other elements can be an effective method to promote gas sensing performances in recent
MOF-Derived years due to the generation of oxygen vacancy defects. In this work, by using MIL-88-Fe as the precursor, Cu-
Cu-doped α-Fe2O3 doped α-Fe2O3 porous spindles have been successfully prepared through a simple solvothermal method. Ac­
Porous spindles
cording to a series of morphological characterizations, α-Fe2O3 still remained the morphology of spindle and
Gas sensor
TEA
exhibited distinctly particle surfaces. The existence of Cu ions restrains the growth of crystalline grains and
enables the α-Fe2O3 spindles to acquire a higher specific surface area and smaller pore sizes. Referring to the gas
sensing properties, 0.5 wt% Cu-doped α-Fe2O3 spindles demonstrated the superior sensitivity towards triethyl­
amine (TEA) at 240 ◦ C with rapid response/recover. And the gas sensing mechanism can be ascribed to the
formation of oxygen vacancy helped by the Cu ions. The more generation of oxygen vacancies means that the
higher amount of molecules tend to be adsorbed on sample’s surfaces, which is beneficial for the enhancement of
gas sensing performances.

1. Introduction
With the rapid development of industries, the explosion of chemical
plants and coal plants were frequently reported and the neglect of gas
detection seriously affects the lifes and properties of people. In partic­
ular, triethylamine (TEA) is one of the common solvents in laboratories
and industries, which can be used in the area of catalyst [1,2] and
antiseptic [3,4]. Whereas, TEA can be a harmful gas for physical heath
like headaches, skin burns and serious pulmonary edema when the
concentration surpassing 10 ppm [5]. In addition, TEA tends to be
exploded when exposing to the flame [6,7]. Therefore, the effective
detection of TEA becomes more and more imperative. From now on,
several of gas sensors have been successfully researched and one of the
gas sensors prepared by metal oxides (such as CuO, In2O3, ZnO, Co2O3,
SnO2 etc) was widely applied into society due to the simple fabrication
process and low power consumption [8–10]. As one of the traditional
n-type semiconductors, α-Fe2O3 possesses the great potential in the
application of gas sensors owing to its unique advantages such as
long-term stability and low cost of production [11,12]. However, some
of inherent defects including high working temperature, low value of
response and poor response/recover rapid hindered its widely applica­
tion. To further promote the gas sensing performances of α-Fe2O3, more
attention should be paid on the investigation of designing and control­
ling the optimized nanostructures of the pristine α-Fe2O3.
According to the previous published works, the preparation of
porous or hollow nanostructures can be an effective method to improve
gas sensing properties of α-Fe2O3. For instance, Jin et al. synthesized the
mesporous α-Fe2O3 hollow spheres through a heterogeneous nucleation
method and gas sensors based on simples demonstrated enhanced
sensitivity towards ethanol, which could be ascribed to plenty of active
sites exposing on surface of the sample [13]. Jun et al. prepared the 3D
porous architectures by controlling the variations in solvent and reac­
tion time, founding that the hierarchically porous nanostructures were
highly beneficial for promoting gas sensing performances [14]. How­
ever, from the above examples, one thing can be clear is that traditional
preparation of porous or hollow nanostructures were complicated. In
recent years, the introduction of metal-organic frameworks (MOFs) can
be an effective approach to synthesis mesporous and hollow nano­
structures, which can be ascribed to their unique strengths of stable,
tunable and multiple morphologies. Meanwhile, compared with the

* Corresponding author.
** Corresponding author.
E-mail addresses: mse_songp@ujn.edu.cn (P. Song), mse_wangq@ujn.edu.cn (Q. Wang).

https://doi.org/10.1016/j.mssp.2020.105510
Received 15 August 2020; Received in revised form 17 September 2020; Accepted 14 October 2020
1369-8001/© 2020 Elsevier Ltd. All rights reserved.

Please cite this article as: Huijun Gao, Materials Science in Semiconductor Processing, https://doi.org/10.1016/j.mssp.2020.105510
H. Gao et al. Materials Science in Semiconductor Processing xxx (xxxx) xxx

metal oxides prepared by other methods, the MOF-derived metal oxides

possess more abundant functional groups, which contributes to the
adsorption of target gases [15–18]. For examples, Lü and cooperative
workers reported MOF-based Co3O4 concave nanocubes by introducing
a self-sacrificed MOFs template and the acquired product possessed a
fast gas-sensing response for ethanol [19]. Due to the plentiful meso­
porous could be acquired by using the MOF templates, the gas diffusion
tends to be easier inset the nanostructures of samples [20]. Therefore,
the introduction MOFs could be considered as a promising way to
enhance response/recover rapid.
In term of gas sensors, the enhanced response value could be ascribed
to the fact that higher amount of free electrons could be accumulated by
oxygen molecules, and the introduction of oxygen vacancy is one of the
common and effective methods to achieve this goal. Qin et al. prepared
the 2D SnS2 containing sulfur vacancies by chemical exfoliation, which
exhibits superior gas sensing performances to ammonia [21]. Mehrabadi
and cooperating partners systematic studied the effect of the amount of
Cu ions on Co3O4, confirming the enhanced gas sensing properties of
CuCo (0.125/0.15) nanocomposites [22]. In addition, the doping of Fig. 1. Synthetic process of pure and Cu-doped α-Fe2O3 porous spindles.
element impurities could facilitate the formation of surface-oxygen va­
cancies and the adsorption of oxygen molecules even at relatively low
working temperature [23]. Wang used an oil bath method to synthesis
the Ce-doped α-Fe2O3 composites and significantly reduced the optimal
temperature from 280 ◦ C to 220 ◦ C [24]. Because of the high catalytic
activity of copper, adding copper to metal oxides can accelerate the
chemical reaction, so that it can increase the surface oxygen adsorption
even at a lower operating temperature, thus improving the gas-sensitive
performance. Rao et al. synthesized Cu: NiFe2O4 thin films by spray
pyrolysis deposition technology, and studied the significant influence of
Cu doping on properties [25]. Patil et al. prepared Cu doped ZnO
nanorods using simple wet chemistry, effectively reducing their oper­
ating temperature [26].
In this article, by using MIL-88-Fe as the template, we prepared the
Cu-doped α-Fe2O3 porous spindles and invested the influence of the Cu
ions content on gas sensing performances. In the detail preparation
process, 0.3 wt% Cu-doped α-Fe2O3 spindles, 0.5 wt% Cu-doped α-Fe2O3
spindles and 1 wt% Cu-doped α-Fe2O3 spindles were synthesized by
simple solvothermal method with subsequently calcination in air. The
pure α-Fe2O3 spindles and Cu-doped α-Fe2O3 spindles were texted by the
system of WS-30A and indicated the enhanced sensitivity and selectivity
of 0.5 wt% Cu-doped α-Fe2O3 spindles to TEA. And by contrast with pure
α-Fe2O3 spindles, the optimal temperature of 0.5 wt% Cu-doped α-Fe2O3
spindles reduced 60 ◦ C. In addition, both pure α-Fe2O3 spindles and Cu-
doped α-Fe2O3 spindles possessed fast response/recover rapid due to the
introduction of MOF precursors.

2. Experimental

2.1. Chemical reagents and materials

All ingredients used were analytical grade and were used without
further purification, which were purchased form Sinopharm Chemical
Reagent Co., Ltd.

2.2. Preparation of Cu-doped α-Fe2O3 porous spindles nanostructures

The prepared method of pure α-Fe2O3 spindles is referred to the

previous work [27] and the detailed steps can be described as follow.
Firstly, 30 ml DMF was slowly poured into 50 ml-contained beaker and
then 15.8 mg (26.3 mg and 52.6 mg) Cu(NO3)2⋅6H2O was added into the
above solvent, respectively. Under the room temperature, the solution
was adequately stirred in order to dissolve the raw materials, which was
called the solution A. Next, 30 ml DMF was measured and poured into
the same sized beaker and 187 mg FeCl3⋅6H2O and 155 mg H2BDC were Fig. 2. (a) XRD patterns of Fe-MIL-88 spindles; (b), (c) FESEM images of Fe-
added into the beaker under the stirring, which is called the solution B. MIL-88 spindles; (d), (f) FESEM images of pure α-Fe2O3 spindles; (e), (g) TEM
By using the pipette, 1 ml solution A was added dropwise into the images of pure α-Fe2O3 spindles.

2
H. Gao et al. Materials Science in Semiconductor Processing xxx (xxxx) xxx

Fig. 3. (a), (b) FESEM images of 0.3 wt% Cu-doped α-Fe2O3 spindles; (c), (d)
FESEM images of 0.5 wt% Cu-doped α-Fe2O3 spindles; (e), (f) FESEM images of
1.0 wt% Cu-doped α-Fe2O3 spindles; (g–i) TEM images of 0.5 wt% Cu-doped
α-Fe2O3 spindles; (j) EDS mapping images of 0.5 wt% Cu-doped
α-Fe2O3 spindles.

solution B with stirring. The mixed solution was heated at 150 ◦ C for 2 h
in a Teflon-lined stainless-steel autoclave. The cooling autoclave was
taken out and the acquired precipitate was washed three times by DMF
and ethanol for purpose of removing unreacted raw materials. After the
dry process (60 ◦ C, 24 h), the prepared Cu-doped MIL-88-Fe was put into
muffle furnace under the condition of 500 ◦ C, 2 h. Finally, the 0.3 wt%,
0.5 wt% and 1.0 wt% Cu-doped α-Fe2O3 porous spindles were success­
fully synthesized.

2.3. Characterization

The microstructures, element states and crystallinity of as-received

pure α-Fe2O3 spindles and Cu-doped α-Fe2O3 spindles were estimated
by powder X-ray diffractometer (XRD, Bruker D8 Advance, λ = 0.15406
nm) using CuKα1 radiation. The surface morphology of the samples
were observed by field-emission scanning electronic microscope
(FESEM, FEI Company, QUANTA FEG 250) and the energy-dispersive X-
ray spectroscopy (EDS) analysis was analyzed by the FESEM attachment.
The more information of the samples was obtained by transmission
electron microscope (TEM, Hitachi H-800). The X-ray photoelectron
spectroscopy (XPS) data were recorded on a Thermo Scientific Escalab
250Xi to determine the elements and its valence of the samples. The
specific surface area was estimated by the Brunauer-Emmett-Teller
(BET) equation based on the nitrogen adsorption isotherm. The
amount of oxygen absorption was texted by O2-Temperature Pro­
grammed Desorption (O2-TPD, Quantachrome Instruments, CBT-1).

3. Results and discussion

3.1. Structural and morphology characteristics

The synthesis strategy of pure α-Fe2O3 spindles and Cu-doped

α-Fe2O3 spindles have been illustrated in Fig. 1. Firstly, by using
FeCl3⋅6H2O as Fe source and H2BDC as organic ligand, Fe-MIL-88
spindles have been prepared by a simple solvothermal method (DMF).
In this preparation process, with the help of balancing anion FeCl-4, the
tri-nuclear Fe3O cluster tended to form the Fe3 MIL-88B [28]. After the
calcination in air, the Fe-MIL-88 was transformed into α-Fe2O3 spindles Fig. 4. XRD patterns of pure α-Fe2O3 spindles and Cu-doped α-Fe2O3 spindles:
with releasing of CO2 and H2O. The synthesis process of Cu-doped (a) full spectra, (b) enlarged spectra; (c) the change of crystallite size as a
α-Fe2O3 spindles was similar to pure α-Fe2O3 spindles. Due to the exis­ function of Cu ions concentration.
tence of Cu element, the growth of α-Fe2O3 crystals was limited to an
extent [29], which contributes to the formation porous nanostructures. nanostructures. As shown in Fig. 2(b, c), the spindles are uniform in size,
According to Fig. 2(a), we can realize that XRD patterns of Fe-MIL-88 approximately 2 μm in length, and the sample is purities. After the
spindles we prepared is similar to the previous work [30] and the main calcination in air, the pure α-Fe2O3 spindles were characterized by SEM
diffraction peaks are located at 9.38◦ , 9.69◦ , 10.68◦ , 12.58◦ , 16.17◦ , and TEM. From Fig. 2(d, f), α-Fe2O3 exhibited the spindle morphology
17.04◦ and 18.83◦ , which confirms the successfully introduction of MOF

3
H. Gao et al.
Fig. 5. XPS spectra of 0.5 wt% Cu-doped α-Fe2O3 spindles: (a) full energy spectrum; (b) Fe 2p binding energy spectrum; (c) O 1s binding energy spectrum; (d) Cu 2p
binding energy spectrum; XPS spectra of pure α-Fe2O3 spindles: (e) Fe 2p binding energy spectrum; (f) O 1s binding energy spectrum.
with size around 1.5 μm in length and the surface of samples is smooth.
There is few impurity nanostructure could be found by SEM character­
ization. The TEM images of pure α-Fe2O3 spindles were exhibited in
Fig. 2(e, g). Due to the introduction of MOF template, the pure α-Fe2O3
spindles are composed by numerous α-Fe2O3 nanoparticles, which
contributes to the gas diffusion and absorption of target gas.
In order to explore the effect of the content of Cu element towards
α-Fe2O3 morphology, Cu-doped α-Fe2O3 spindles were characterized by
SEM and exhibited in Fig. 3(a-f). By being compared by each other,
although they all possess the spindle nanostructures, it is obvious that
the morphology of 0.5 wt% Cu-doped α-Fe2O3 spindles is superior
because 0.5 wt% Cu-doped α-Fe2O3 spindles exhibit distinctly particle
surface without destroying the spindle nanostructure. Therefore, we
used TEM characterization to research the inside morphology of 0.5 wt%
Cu-doped α-Fe2O3 spindles. From Fig. 3(g and h), the size of spindles in
length is reduced to 1 μm and there are plenty of pore nanostructures
existing in this sample. In Fig. 3(i), the lattice fringe of α-Fe2O3 is about
0.346 nm, referring to the (012) plane of rhombohedral α-Fe2O3 struc­
ture (JCPDS card No. 33–0664). Fig. 3(j) is EDS mapping images of 0.5
wt% Cu-doped α-Fe2O3 spindles. It is clearly that the sample is composed
by three elements and the doped content of Cu ions is not high. Mean­
while, elements are uniformly distributed in 0.5 wt% Cu-doped α-Fe2O3
spindles.
The XRD pattern of pure α-Fe2O3 spindles and Cu-doped α-Fe2O3
spindles were illustrated in Fig. 4(a). Among this, all samples were
switched well with the α-Fe2O3 (JCPDS No. 33–0664), which illustrates
that the existence of Cu ions does not change the type of α-Fe2O3 crystal.
At the same time, no peaks of CuO could be found in this XRD pattern
owing to the low content of Cu ions. To further study the influence of Cu
Fig. 6. N2 adsorption-desorption isotherm curve and the pore size distribution curve of (a) 0.5 wt% Cu-doped α-Fe2O3 spindles and (b) pure α-Fe2O3 spindles.
4
Materials Science in Semiconductor Processing xxx (xxxx) xxx
ions on crystal nanostructure of simples, one peak of (110) was enlarged
and the phenomenon of peak position drift could be observed. From
Fig. 4(b), with the increasing content of Cu ions, the peak position shifts
to a higher angle to some extent, suggesting the successfully incorpo­
ration of Cu ions in pure α-Fe2O3 spindles. The reason why is that the
existence of Cu ions results in the lattice deformation owing to the
different ionic radius [31]. Fig. 4(c) is the α-Fe2O3 grain size corre­
sponding to the Cu ion doped with different concentrations. It can be
seen from the figure that when the concentration of Cu ion is 0 wt%, 0.3
wt%, 0.5 wt%, and 1.0 wt%, the corresponding grain sizes of α-Fe2O3 are
31.8, 28.3, 26.2, and 24.2, respectively. It is obvious that the crystalline
size of α-Fe2O3 reduces dramatically with the increasing concentration
of Cu ions, indicating the growth of crystalline grain was restrained by
Cu ions.
The XPS spectra of pure α-Fe2O3 spindles and 0.5 wt% Cu-doped
α-Fe2O3 spindles have been exhibited in Fig. 5. The full spectrum
(Fig. 5(a)) indicates that there are three elements existing in samples and
no other impurity elements could be found. Fig. 5(b) is the Fe 2p spec­
trum of 0.5 wt% Cu-doped α-Fe2O3 spindles and two main spectrum
peaks are accordance with Fe 2p3/2 and Fe 2p1/2 of α-Fe2O3. The same Fe
2p spectrum can be found in pure α-Fe2O3 spindles (Fig. 5(e)).
Furthermore, O element possesses three states in Fig. 5(c): the lattice
oxygen (Olatt), oxygen vacancy regions (Ovac) and the surface-
chemisorbed oxygen (Oads). By contrasting with α-Fe2O3 simples
(Fig. 5(f)), the number of oxygen vacancy and surface-chemisorbed
oxygen increases from 14.7% to 47.7%, which enhances to the gas
sensing properties. According to the Cu 2p spectrum in Fig. 5(d), three
main peaks located at 937.6 eV, 945.4 eV and 957.8 eV are referred to
Cu 2p3/2, Cu CT and Cu 2p1/2, which further confirms the existence of Cu
H. Gao et al.
Fig. 7. (a) Sensing response to 100 ppm TEA gas versus different working
temperature (160–340 ◦ C) and (b) Dynamic response-recovery curves (100 ppm
TEA) of pure α-Fe2O3 spindles and Cu-doped α-Fe2O3 spindles.
ions in samples.
To research the BET specific surface area and pore size distribution of
samples, pure α-Fe2O3 spindles and 0.5 wt% Cu-doped α-Fe2O3 spindles
were evaluated by the BET characterization (Fig. 6). From the N2
adsorption-desorption isotherms, these isotherms belong to the IV type
and the hysteresis loop located at 0.7–1.0 P/P0 could be noticed,
meaning the successful preparation of mesoporous nanostructures. By
contrast with the pure α-Fe2O3 spindles, the specific surface area of 0.5
wt% Cu-doped α-Fe2O3 spindles increased from 11.6 to 25.3 m2/g.
Meanwhile, according to the pore size distribution (inset of Figs. 6), 0.5
wt% Cu-doped α-Fe2O3 spindles contain a minimum pore size at 2.3 nm
and a maximum at 20.8 nm, which could be ascribed to the porous
nanoparticles and the pack of them. According to the previous work, the
connected channels mesoscale (2–50 nm) pore sizes in mesoporous
nanostructures are favor for the gas diffusion and adsorption [32]. Due
to the Knudsen diffusion, the penetration of gas molecules to inner
nanostructure tends to be facile [33,34]. The phenomenon of facile
penetration is one of significant factors for gas sensing performances,
leading to a rapid response and recover of simples [35].
3.2. 2 Gas sensing properties
The working temperature is essential for gas sensors, which will
5
Materials Science in Semiconductor Processing xxx (xxxx) xxx
affect the reaction kinetics and adsorption of surface oxygen molecules
[36]. Therefore, the working temperature of pure α-Fe2O3 spindles and
Cu-doped α-Fe2O3 spindles has been researched at the range from
160–340 ◦ C in Fig. 7(a). From this figure, gas sensors based on Cu-doped
α-Fe2O3 spindles demonstrated low working temperatures towards TEA
than the gas sensor prepared by pure α-Fe2O3 spindles. In particular, 1.0
wt% Cu-doped α-Fe2O3 spindles demonstrated a lowest optimal tem­
perature than others towards TEA (200 ◦ C), which reduced 100 ◦ C
comparing with pure α-Fe2O3 spindles. In addition, the introduction of
Cu ions is beneficial for promoting the sensitivity of the α-Fe2O3 spindles
from Fig. 7(b). By contrast with other Cu-doped α-Fe2O3 spindles, the
gas sensor based on 0.5 wt% Cu-doped α-Fe2O3 spindles exhibited a
superior sensitivity (31.7, 100 ppm), which was 2.7 times in response
higher than primitive α-Fe2O3 spindles. Meanwhile, both of pure
α-Fe2O3 spindles and Cu-doped α-Fe2O3 spindles possessed rapid
response and recover process (2 s and 7 s) due to the introduction of
MOF template. According to the above discussion, 0.5 wt% Cu was
determined the optimal doping content and the 0.5 wt% Cu-doped
α-Fe2O3 spindles were chosen to research their other gas sensing per­
formances by the further text.
Concentration-dependent response curves of primitive α-Fe2O3 sim­
ples and 0.5 wt% Cu-doped α-Fe2O3 spindles were plotted in Fig. 8(a).
Gas sensors based on simples were exposed to TEA with the concen­
tration ranging from 10 ppm to 1000 ppm. It is distinctly that the
response value of 0.5 wt% Cu-doped α-Fe2O3 spindles increased faster
and showed enhanced sensitivity at each concentration. As shown in
Fig. 8(b), the fitting line slope of 0.5 wt% Cu-doped α-Fe2O3 spindles
(0.70) was higher than pure α-Fe2O3 spindles (0.25). However, both of
them demonstrated a well linear relationship between log (S-1) and log
(C) towards TEA. To investigate the stability of gas sensors, 0.5 wt% Cu-
doped α-Fe2O3 spindles were texted by the three reversible cycles and
exhibited smaller fluctuations than pure α-Fe2O3 spindles in Fig. 8(c),
which indicated the 0.5 wt% Cu-doped α-Fe2O3 spindles possessed a
superior repeatability and stability. As for the selectivity of 0.5 wt% Cu-
doped α-Fe2O3 spindles, six different gasses with the concentration of
100 ppm were introduced and the result was indicated in Fig. 8(d).
Expecting the TEA, the gas sensor prepared by 0.5 wt% Cu-doped
α-Fe2O3 spindles showed relatively low response value, manifesting
the good selectivity of gas sensors. Compared with the pure α-Fe2O3
spindles, the existence of Cu ions contributes to the improving response
for most targeted gases, which verifies the positive effect of Cu ions in
gas sensors. In Table 1, we also list some gas-sensitive materials with
good properties of triethylamine, and further illustrate that the 0.5 wt%
Cu-doped α-Fe2O3 spindle-based gas sensor is very promising in the
detection of trimethylamine [37–41] (see Fig. 9).
3.3. 3 Gas sensing mechanism
Referring to the above discussion, the gas sensor based on 0.5 wt%
Cu-doped α-Fe2O3 spindles exhibited enhanced gas sensing perfor­
mances and the mechanism could be described at follow. As is known to
all, the electron depletion layer of α-Fe2O3 could be changed when
exposing to different atmosphere, which results in the variation of
resistance [42]. In ambient air, oxygen molecules are inclined to be
adsorbed by the α-Fe2O3 surface and extract free electrons from the
conduction band to form oxygen species (O−2 , O− and O2− ). Therefore,
the loss of free electrons contributes to the generation of depletion layer
on α-Fe2O3 surfaces and the sample can acquire a high resistance in air.
After the injection of the TEA, the target gas could be easy to diffuse
through the porous spindles and react with ionic oxygen species. After
that, the releasing electrons will return to the conduction band and
recover the electrical conductivity. The detailed reactions were
demonstrated at follow [43–45]:
O2(gas) → O2(ads) (4)
H. Gao et al. Materials Science in Semiconductor Processing xxx (xxxx) xxx

Fig. 8. (a) Concentration-dependent response curves

of pure α-Fe2O3 spindles and 0.5 wt% Cu-doped
α-Fe2O3 spindles to 10–1000 ppm TEA; (b) The cor­
responding log (S-1) vs. log (C) of gas sensors based
on pure α-Fe2O3 spindles and 0.5 wt% Cu-doped
α-Fe2O3 spindles; (c) Reproducibility of pure
α-Fe2O3 spindles and 0.5 wt% Cu-doped α-Fe2O3
spindles based on sensors upon exposure (3 cycles) to
100 ppm TEA gas; (d) Sensing responses to different
gases (100 ppm) of pure α-Fe2O3 spindles and 0.5 wt
% Cu-doped α-Fe2O3 spindles.

O2(ads) + e− → O−2 (ads) (5)

O−2 (ads) + e− → 2O− (ads) (6)

− − 2−
O (ads) + e → O (ads) (7)

Et2N–CH2–CH3 (ads) + 39/2O (ads) → N2 + 6CO2 + 15/2H2O + 39/2e (8)

− −

In addition, the enhanced performances could be ascribed to the

existence of Cu ions. Firstly, after the successful doping of Cu ions in
α-Fe2O3 spindles, Fe3+ tends to be substituted and some of lattice defects
will generate due to the mismatch of ionic radius and valence state. In
order to release lattice distortion energy, oxygen vacancies are gener­
ated according to the Kröger-Vink notations (2CuO → 2Cu’Fe+V⋅⋅O+2OO)
[5,46], which enables the 0.5 wt% Cu-doped α-Fe2O3 spindles to acquire
a higher amount of oxygen vacancies than pure α-Fe2O3 spindles.
Therefore, more donor sites generating on the surface of 0.5 wt%
Cu-doped α-Fe2O3 spindles make it easy to adsorb the oxygen molecules
under the low operating temperature, indicating the better sensitivity
and lower optimal temperature of 0.5 wt% Cu-doped α-Fe2O3 spindles
than pure α-Fe2O3 spindles [23]. Otherwise, the doping of Cu ions may
hinder the growth of α-Fe2O3 grains to some extent, which is verified by
the XRD characterization. The fined grains are beneficial for exposing
more active sites on surfaces and promoting the gas sensing response
[47]. However, when the doping amount exceeded a certain scope, the
generation of CuO would replace the substituted Cu ions and degrade
the sensitivity of samples [48].

Fig. 9. Schematic diagram of possible gas sensing mechanisms of Cu-doped 4. Conclusion

α-Fe2O3 porous spindles.
In summary, by introducing the MIL-88-Fe precursor, Cu-doped
α-Fe2O3 porous spindles were synthesized by a facile solvothermal
Table 1 method with subsequently calcination process. After the corporation of
Compared TEA-sensing performance of different sensors. Cu ions, the size of α-Fe2O3 spindles deceased from 1.5 μm to 1 μm and
Sensor material T TEA Response Res/ Ref the Cu-doped α-Fe2O3 spindles s possessed the smaller crystalline size
(oC) (ppm) (Ra/Rg) Rec (s) from the SEM and XRD characterizations, which increased the specific
Cu-doped α-Fe2O3 240 100 1.7 2/7 This surface area and decreased the pore size and contributes to the diffusion
spindles work and adsorption of target gas. In addition, the existence of Cu ions
SnO2 flowerlike 350 100 4 [37]
<6/<6
contributed the generation of oxygen vacancy defects and active sites on
V2O5 hollow sphere 370 100 7.2 40/125 [38]
Sea urchin-like 350 100 <20 8/18 [39] the surface of simples. Therefore, Cu-doped α-Fe2O3 spindles exhibited
Fe2O3 enhanced sensitivity to TEA and lower working temperature than pure
α-Fe2O3 microrods 275 500 41 25/55 [40] α-Fe2O3 spindles. In addition, the content of Cu ions was also essential
MoO3 microsheets 275 100 27.1 30/50 [41] for the gas sensing performances and after the comparison with others,

6
H. Gao et al.
0.5 wt% Cu-doped α-Fe2O3 spindles showed the superior sensitivity to
100 ppm TEA at low optimal temperature. From the above discussion,
we notice that the corporation of other element is an effective method
for enhancing properties in the area of gas sensors.
CRediT authorship contribution statement
Huijun Gao: Methodology, Validation, Investigation, Data curation,
Writing - original draft. Yuzhen Ma: Methodology, Validation, Inves­
tigation, Data curation. Peng Song: Conceptualization, Writing - review
& editing, Project administration. Zhongxi Yang: Conceptualization. Qi
Wang: Writing - review & editing, Project administration.
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.
Acknowledgement
This work was financially supported by National Natural Science
Foundation of China (No. 61102006), and Natural Science Foundation
of Shandong Province, China (No. ZR2018LE006 and ZR2015EM019).
References
[1] H. Rao, L.C. Schmidt, J. Bonin, M. Robert, Visible-light-driven methane formation
from CO2 with a molecular iron catalyst, Nature 548 (2017) 74–77.
[2] D.K. Mahapatra, V.G. Ugale, R.S. Shivhare, Murrayanine-1, 3, 4-oxadiazole-uracil
hybrid: the emerging anti-inflammatory candidate, Int. J. Pharma Sci. Res. 9
(2018) 99–102.
[3] J. Song, S.J.A. Remmers, J. Shao, E. Kolwijck, X.F. Walboomers, J.A. Jansen, C.
G. Leeuwenburgh, F. Yang, Antibacterial effects of electrospun chitosan/poly
(ethylene oxide) nanofibrous membranes loaded with chlorhexidine and silver,
Nanomed-Nanotechnol. 12 (2016) 1357–1364.
[4] T.T. Zhou, R. Zhang, Y.B. Wang, T. Zhang, MOF-derived 1D α-Fe2O3/NiFe2O4
heterojunction as efficient sensing materials of acetone vapors, Sensor. Actuator. B
Chem. 281 (2019) 885–892.
[5] T. Cai, L. Chen, Q. Ren, S. Cai, J. Zhang, The biodegradation pathway of
trithylamine and its biodegradation by immobilized arthrobacter protophormiae
cells, J. Hazard Mater. 186 (2011) 59–66.
[6] C. Zhao, H. Gong, W. Lan, R. Ramachandran, H. Xu, S. Liu, F. Wang, Facile
synthesis of SnO2 hierarchical porous nanosheets from graphene oxide sacrificial
scaffolds for high-performance gas sensors, Sensor. Actuator. B Chem. 258 (2018)
492–500.
[7] L. Liu, Y.T. Zhao, P. Song, Z.X. Yang, Q. Wang, Ppb level triethylamine detection of
yolk-shell SnO2/Au/Fe2O3 nanoboxes at low-temperature, Appl. Surf. Sci. 476
(2019) 391–401.
[8] P. Wang, Z.K. Zheng, X.L. Cheng, L. L Sui, S. Gao, X.F. Zhang, Y.M. Xu, H. Zhao, L.
H. Huo, Ionic liquid-assisted synthesis of α-Fe2O3 mesoporous nanorod arrays and
their excellent trimethylamine gas-sensing properties for monitoring fish freshness,
J. Mater. Chem. A. 5 (2017) 19846–19856.
[9] J. Wang, Z. Li, S. Zhang, S. Yan, B. Cao, Z. Wang, Y. Fu, Enhanced NH3 gas-sensing
performance of silica modified CeO2 nanostructure based sensors, Sensor. Actuator.
B Chem. 255 (2018) 862–870.
[10] Y.M. Sabri, A.E. Kandjani, S.S.A.A.H. Rashid, C.J. Harrison, S.J. Ippolito, S.
K. Bhargava, Soot template TiO2 fractals as a photoactive gas sensor for acetone
detection, Sensor. Actuator. B Chem. 275 (2018) 215–222.
[11] J.S. Jang, W.T. Koo, S.J. Choi, I.D. Kim, Metal organic framework-templated
chemiresistor: sensing type transition from P-to-N using hollow metal oxide
polyhedron via galvanic replacement, J. Am. Chem. Soc. 139 (2017)
11868–11876.
[12] H.X. Yu, S. Gao, X.L. Cheng, P. Wang, X.F. Zhang, Y.M. Xu, H. Zhao, L.H. Huo,
Morphology controllable Fe2O3 nanostructures derived from Fe-based metal-
organic frameworks for enhanced humidity sensing performances, Sensor.
Actuator. B Chem. 297 (2019) 126744.
[13] C. Jin, C. Ge, X. Gang, G. Peterson, Z.Y. Jian, Y.X. Wei, K.X. Zhu, Influence of
nanoparticle size on ethanol gas sensing performance of mesoporous α-Fe2O3
hollow spheres, Mater. Sci. Eng. B. 224 (2017) 158–162.
[14] J. Zhang, S. Wang, M. Xu, Y. Wang, B. Zhu, S. Zhang, W. Huang, S. Wu,
Hierarchically porous ZnO architectures for gas sensor application, Cryst. Growth
Des. 9 (2009) 3532–3537.
[15] C.Z. Liao, M. Zhang, L.Y. Niu, Z.J. Zheng, F. Yan, Organic electrochemical
transistors with graphene-modified gate electrodes for highly sensitive and
selective dopamine sensors, J. Mater. Chem. 2 (2014) 191–200.
[16] X.G. Wang, Q. Cheng, Y. Yu, X.Z. Zhang, Controlled nucleation and controlled
growth for size predicable synthesis of nanoscale metal-organic frameworks
7
Materials Science in Semiconductor Processing xxx (xxxx) xxx
(MOFs): a general and scalable approach, Angew. Chem. Int. Ed. 57 (2018)
7836–7840.
[17] C. Hou, D. Zhao, Y. Wang, S.F. Zhang, S.Y. Li, Preparation of magnetic Fe3O4/
PPy@ZIF-8 nanocomposite for glucose oxidase immobilization and used as glucose
electrochemical biosensor, J. Electroanal. Chem. 822 (2018) 50–56.
[18] Q. Wei, J. Sun, P. Song, J. Li, Z.X. Yang, Q. Wang, MOF-derived α-Fe2O3 porous
spindle combined with reduced graphene oxide for improvement of TEA sensing
performance, Sensor. Actuator. B Chem. 304 (2020) 127306.
[19] Y. Lü, W. Zhan, Y. He, Y.T. Wang, X.J. Kong, Q. Kuang, Z.X. Xie, L.S. Zheng, MOF-
templated synthesis of porous Co3O4 concave nanocubes with high specific surface
area and their gas sensing properties, ACS Appl. Mater. Interfaces 6 (2014)
4186–4195.
[20] Y. Wang, D. Zhao, Beyond Equilibrium: Metal–Organic Frameworks for Molecular
Sieving and Kinetic Gas Separation, Crystal Growth & Design, 2017.
[21] Z. Qin, K. Xu, H. Yue, H. Wang, J. Zhang, C. Ouyang, C. Xie, D. Zeng, Enhanced
room-temperature NH3 gas sensing by 2D SnS2 with sulfur vacancies synthesized
by chemical exfoliation, Sensor. Actuator. B Chem. 262 (2018) 771–779.
[22] Z.S. Mehrabadi, A. Ahmadpour, N. Shahtahmasebi, Mohagheghi Synthesis and
characterization of Cu doped cobalt oxide nanocrystals as methane gas sensors,
Phys. Scripta 84 (2011), 015801.
[23] P.S. Kolhe, S.G. Kulkarni, N. Maiti, K.M. Sonawane, Effect of Cu doping
concentration on H2S gas sensing properties of Cu-doped SnO2 thin films, Appl.
Phys. A-Mater. 125 (2019) 372.
[24] X. Wang, T. Wang, G. Si, Y. Li, S. Zhang, X. Deng, X. Xu, Oxygen vacancy defects
engineering on Ce-doped α-Fe2O3 gas sensor for reducing gases, Sensor. Actuator. B
Chem. 302 (2020) 127165.
[25] P. Rao, R.V. Godbole, S. Bhagwat, Copper doped nickel ferrite nano-crystalline thin
films: a potential gas sensor towards reducing gases, Mater. Chem. Phys. 171
(2016) 260–266.
[26] V.L. Patil, S.A. Vanalakar, N.L. Tarwal, A.P. Patil, T.D. Dongale, J.H. Kim, P.
S. Patil, Construction of Cu doped ZnO nanorods by chemical method for Low
temperature detection of NO2 gas, Sens. Actuators A Chem. 299 (2019) 111611.
[27] X. Xu, R. Cao, S. Jeong, J. Cho, Spindle-like mesoporous α-Fe2O3 anode material
prepared from MOF template for high-rate lithium batteries, Nano Lett. 12 (2012)
4988–4991.
[28] T.T. Zhou, R. Zhang, Y.B. Wang, T. Zhang, MOF-derived 1D α-Fe2O3/NiFe2O4
heterojunction as efficient sensing materials of acetone vapors, Sensor. Actuator. B
Chem. 281 (2019) 885–892.
[29] X. Xu, J. Sun, H. Zhang, et al., Effects of Al doping on SnO2 nanofibers in hydrogen
sensor, Sensor. Actuator. B Chem. 160 (2011) 858–863.
[30] T.A. Vu, G.H. Le, H.T. Vu, K.T. Nguyen, Highly photocatalytic activity of novel Fe-
MIL-88B/GO nanocomposite in the degradation of reactive dye from aqueous
solution, Mater. Res. Express 4 (2017) 35–38.
[31] Y. Cheng, Y. He, S. Li, Y. Wang, Y. Zhao, Y. Li, H. Li, L. Liu, Ultra-sensitive and
selective acetone gas sensor with fast response at low temperature based on Cu-
doped α-Fe2O3 porous nanotubes, J. Mater. Sci. Mater. Electron. 29 (2018).
[32] X. Wang, T.K. Wang, G.K. Si, Y. Li, S.W. Zhang, X.L. Deng, X.J. Xu, Oxygen vacancy
defects engineering on Ce-doped α-Fe2O3 gas sensor for reducing gases, Sensor.
Actuator. B Chem. 302 (2020) 127165.
[33] T. Wang, I. Can, S. Zhang, J. He, P. Sun, F. Liu, G. Lu, Self-assembly template
driven 3D inverse opal microspheres functionalized with catalyst nanoparticles
enabling a highly efficient chemical sensing platform, ACS Appl. Mater. Interfaces
10 (2018) 5835–5844.
[34] J. Ma, Y. Ren, X. Zhou, L. Liu, Y. Zhu, X. Cheng, P. Xu, X. Li, Y. Deng, D. Zhao, Pt
nanoparticles sensitized ordered mesoporous WO3 semiconductor: gas sensing
performance and mechanism Study, Adv. Funct. Mater. 28 (2018) 1705268.
[35] P. Innocenzi, L. Malfatti, Mesoporous thin films: properties and applications,
Chem. Soc. Rev. 42 (2013) 4198–4216.
[36] D. Han, P. Song, S. Zhang, H.H. Zhang, Q. Xu, Q. Wang, Enhanced methanol gas-
sensing performance of Ce-doped In2O3 porous nanospheres prepared by
hydrothermal method, Sens. Actuators, B 216 (2015) 488–496.
[37] B. Liu, L.H. Zhang, H. Zhao, Synthesis and sensing properties of spherical
flowerlike architectures assembled with SnO2 submicron rods, Sens. Actuators, B
173 (2012) 643–651.
[38] M.Z. Wu, X.F. Zhang, S. Gao, Construction of monodisperse vanadium pentoxide
hollow spheres via a facile route and triethylamine sensing property,
CrystEngComm 15 (2013) 10123–10131.
[39] F.H. Zhang, H.Q. Yang, X.L. Xie, Controlled synthesis and gas-sensing properties of
hollow sea urchin-like -Fe2O3 nanostructures and -Fe2O3 nanocubes, Sens.
Actuators, B 141 (2009) 381–389.
[40] W.H. Jiang, D.D. Wei, S.F. Zhang, The facile synthesis of MoO3 microsheets and
their excellent gas-sensing performance toward triethylamine: high selectivity,
excellent stability and superior repeatability, New J. Chem. 42 (2018) 15111.
[41] G. Sun, H.L. Chen, Y.W. Li, Synthesis and triethylamine sensing properties of
mesoporous α-Fe2O3 microrods, Mater. Lett. 178 (2016) 213–216.
[42] X.B. Li, Q.Q. Zhang, S.Y. Ma, G.X. Wan, F.M. Li, X.L. Xu, Microstructure
optimization and gas sensing improvement of ZnO spherical structure through
yttrium doping, Sensor. Actuator. B Chem. 195 (2014) 526–533.
[43] S. Zhang, B. Zhang, G. Sun, Y. Li, B. Zhang, Y. Wang, J. Cao, Z. Zhang, One-step
synthesis of Ag/SnO2/rGO nanocomposites and their trimethylamine sensing
properties, Mater. Res. Bull. 2114 (2019) 61–67.
[44] P. Song, Q. Wang, Z.X. Yang, Preparation, characterization and acetone sensing
properties of Ce-doped SnO2 hollow spheres, Sens. Actuators, B 173 (2012)
839–846.
H. Gao et al.
[45] L. Guo, C. Wang, X. Kou, N. Xie, F. Liu, H. Zhang, X. Liang, Y. Gao, Y. Sun, X. Chuai,
G. Lu, Detection of triethylamine with fast response by Al2O3/α-Fe2O3 composite
nanofibers, Sensor. Actuator. B Chem. 266 (2018) 139–148.
[46] S. Bose, S. Chakraborty, B.K. Ghosh, D. Das, A. Sen, H.S. Maiti, Methane sensitivity
of Fe-doped SnO2 thick films, Sensor. Actuator. B Chem. 105 (2005) 346–350.
Materials Science in Semiconductor Processing xxx (xxxx) xxx
[47] X. Xu, J. Sun, H. Zhang, Effects of Al doping on SnO2 nanofibers in hydrogen sensor
160 (2011) 858–863.
[48] J.P. Cheng, B.B. Wang, M.G. Zhao, F. Liu, X.B. Zhang, Nickel-doped tin oxide
hollow nanofibers prepared by electrospinning for acetone sensing, Sensor.
Actuator. B Chem. 190 (2014) 78–85.