Multishelled Hollow Structures of Yttrium Oxide for the Highly Selective and Ultrasensitive Detection of Methanol

Article abstract of DOI:10.1002/smll.201804688

Methanol is extremely harmful to human health, since it is oxidized slowly and can accumulate in the human body. Therefore, it is essential to develop a methanol gas sensing technology with high sensitivity and selectivity for use in environmental monitoring and healthcare. In this work, a simple and low-cost sensor based on a Y₂O₃ multishelled hollow structure (YMSH) to selectively detect methanol with an ultrasensitive limit of detection (71 ppb) is developed. The unique multishelled hollow structure with a large surface area and exposed {222} facets makes an important contribution to the ultrasensitive detection of methanol, which is further confirmed by subsequent theoretical simulations. Moreover, in situ Fourier transform infrared spectra verify that CO₂ is the final product, which indicates a high catalytic activity of the YMSHs toward methanol oxidation. Interestingly, the sensor can also be applied to liquor samples that are mixtures of ethanol, methanol, and water, which provides a facile way to detect methanol in wines. This sensor represents a unique and highly sensitive means to detect methanol, which has great promise for potential application in environmental monitoring and food safety inspection.

Full text of DOI:10.1002/smll.201804688

FULL PAPER
Methanol Detection
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Multishelled Hollow Structures of Yttrium Oxide for the
Highly Selective and Ultrasensitive Detection of Methanol
Jianzhong Zheng, Tingmei Zhang, Huajie Zeng, Wei Guo, Bo Zhao, Yinghui Sun,
Youyong Li, and Lin Jiang*
is extremely harmful to human health
Methanol is extremely harmful to human health, since it is oxidized slowly
and can accumulate in the human body. Therefore, it is essential to develop
a methanol gas sensing technology with high sensitivity and selectivity for
use in environmental monitoring and healthcare. In this work, a simple and
low-cost sensor based on a Y O multishelled hollow structure (YMSH) to
selectively detect methanol with an ultrasensitive limit of detection (71 ppb)
is developed. The unique multishelled hollow structure with a large surface
area and exposed {222} facets makes an important contribution to the ultra-
sensitive detection of methanol, which is further confirmed by subsequent
theoretical simulations. Moreover, in situ Fourier transform infrared spectra
because it paralyzes the central nervous
system and damages the optic nerve and
[
15,16]
retina, causing blindness and death.
According to experimental results on ani-
mals, staying in a 35 ppm methanol steam
for 30–60 min is dangerous for people.
Worse still, methanol is different from
other alcohols, since it is oxidized slowly
and can accumulate in the human body.
Hence, it is essential to detect methanol
with high sensitivity and selectivity for
environmental monitoring and healthcare
purposes.
2
3
verify that CO is the final product, which indicates a high catalytic activity of
2
the YMSHs toward methanol oxidation. Interestingly, the sensor can also be
applied to liquor samples that are mixtures of ethanol, methanol, and water,
which provides a facile way to detect methanol in wines. This sensor repre-
sents a unique and highly sensitive means to detect methanol, which has
great promise for potential application in environmental monitoring and food
safety inspection.
3
D hierarchical-structured metal oxides
have drawn wide attention in gas-sensing
technology research in recent years due to
their high surface area and abundance of
accessible active sites, which can not only
efficiently enhance molecular gas diffu-
sion but also provide a number of active
sites for enhancing the selectivity and cata-
[
17–25]
lytic activity.
To date, various 3D hier-
archical-structured metal oxides with desirable morphologies
and structures have been designed and synthesized to improve
1
. Introduction
[
26–28]
[29–31]
The energy crisis has become one of the most important prob-
the performance of gas sensors, such as ZnO,
Co O ,
3 4
lems facing the world today.[
1–3]
To meet increasing energy and
SnO2,
[32,33]
WO3,
[34–36]
and In O .
[37–39]
Meanwhile, the exposed
2
3
environmental demands, methanol fuel cells are considered to
crystals of 3D hierarchical-structured metal oxides have also
be one of the best choices for clean and efficient power genera-
had a pivotal effect on the sensitivity and selectivity of gas
tion.[
4–6]
As the simplest alcohol, methanol is the most prom-
ising fuel additive candidate for internal combustion engines
since it is inexpensive and easily handled, transported, and
sensors.
[40–42]
A number of methods based on 3D hierarchical
[
43]
[44]
[45]
structures, such as diode, fluorescence, luminescence,
[
46]
and ellipsoidal nanospheres, have been employed for meth-
anol detection. However, methanol sensors based on electrical
resistance can achieve a detection limit of 5 ppm, but the selec-
tivity of detection is always too low to meet the requirements of
stored.[
7–9]
Moreover, methanol is present in the atmosphere,
[10]
[11]
deep-subsurface environments,
and even in interstellar
space,[ which makes it one of the most abundant compounds
12]
[13]
[46]
and the most prevalent of the gases. However, experimentally
practical applications. Therefore, detection of methanol with
detecting trace amounts of methanol around high-mass protos-
both high sensitivity and selectivity remains a significant chal-
lenge. Moreover, wines unavoidably contain low concentrations
of methanol, a reliable methanol sensor for selectively detecting
methanol in mixed methanol and ethanol solutions is lacking
as well. Among the oxide materials, yttrium oxide (Y O ) with
tellar disks is largely unsuccessful.[
13,14]
Additionally, methanol
Dr. J. Zheng, T. Zhang, H. Zeng, W. Guo, B. Zhao, Prof. Y. Sun,
Prof. Y. Li, Prof. L. Jiang
Jiangsu Key Laboratory for Carbon-Based Functional
Materials and Devices
Institute of Functional Nano and Soft Materials (FUNSOM)
Soochow University
Suzhou 215123, Jiangsu, P. R. China
E-mail: ljiang@suda.edu.cn
2
3
rare earth elements is one of the most attractive candidates
for use in methanol sensors because of its excellent adsorp-
[
47–52]
tion selectivity and high thermal and chemical stabilities.
However, thus far, desirable 3D hierarchical-structured yttrium
oxide-based methanol gas sensors have never been proposed.
Herein, we have designed and fabricated a sensor based on
a 3D hierarchical yttrium oxide multishelled hollow structure
DOI: 10.1002/smll.201804688
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(YMSHs) to detect methanol with high selectivity and an ultra- 2. Results and Discussion
sensitive limit (71 ppb). The cataluminescence (CTL) method
is used for rapid identification of methanol, which provides a
stable response using simple low-cost devices. The multishelled
structure and the internal void space of 3D hierarchical yttrium
oxide result in a larger surface area and more active sites than
those of normal solid structures, which make important contri-
butions to the ultrasensitive detection of methanol. Both experi-
mental and simulation results confirm that the abundant {222}
facets of the yttrium oxide multishelled hollow structures play a
key role in the highly selective detection of methanol. Moreover,
to identify the mechanism of the YMSH-dependent methanol
CTL reaction, the final products of the reaction of methanol on
the surface of the YMSHs were monitored by in situ Fourier
transform infrared (FTIR) characterization techniques. Inter-
estingly, this sensor can also be applied to liquor samples that
are a mixture of ethanol, methanol, and water, which provides a
facile way to detect methanol in wines. This sensor represents a
unique and highly sensitive method to detect methanol, which
has great promise for potential application in environmental
monitoring and food safety inspection.
We designed a one-step hydrothermal method to produce
3+
carbon microspheres containing yttrium (Y ) ions and then
obtained the 3D hierarchical yttrium oxide multishelled hollow
structures through calcination, as shown in Figure 1a. Uniform
carbon microspheres containing Y3 ions with a diameter of
≈2.0 µm were prepared from a mixed solution including urea,
yttrium chloride, and glucose using hydrothermal methods
(Figure S1a, Supporting Information). An obvious diffraction
peak in the X-ray powder diffraction (XRD) pattern was observed
at ≈18° (Figure S1b, Supporting Information), which is charac-
teristic of an amorphous carbon matrix. Meanwhile, the ele-
mental mapping results of the carbon microspheres show that
the elements of C, N, O, and Y were homogeneously distrib-
uted throughout the microspheres (Figure S1c,d, Supporting
Information). The desirable highly crystalline yttrium oxide
spheres with hierarchical multishelled hollow structures were
constructed after annealing the carbon microspheres at 550 °C
in air. As shown in Figure 1b, the XRD pattern of the yttrium
oxide multishelled hollow structures revealed that this material
+
Figure 1. a) Scheme for the formation process of the yttrium-oxide multishelled hollow structure, b) XRD diffraction pattern, c) SEM image, d) TEM
image, e) HRTEM image, f) SAED pattern, and g) HAADF-STEM image with the elemental mapping images and line scanning image of the YMSHs.
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is in the cubic Y O phase (JCPDS Card No. 65-3178). Addition-
with glucose inhibits the formation of the carbon microspheres
and multishelled structures cannot be generated (Figure S3, Sup-
porting Information). The introduced urea exhibits a stronger
coordination with the Y3 ions compared to that of glucose, which
results in the formation of carbon microspheres and the resultant
multishelled hollow structures. Therefore, urea plays a crucial
role in fabricating materials with multishelled structural mor-
phologies by one-step hydrothermal treatment.
2
3
ally, an obvious (222)-plane peak was observed, which verifies
the abundance of {222} crystal facets in the YMSHs. Scanning
electron microscopy (SEM) images (Figure 1c) show that the
multishelled hollow structures have a sharp contrast between
the shells and hollow interiors, and their sizes are uniform
with an average diameter of ≈900 nm. The multishelled hollow
structures are further illustrated by the transmission electron
microscopy (TEM) image (Figure 1d). The high-resolution TEM
image (Figure 1e) reveals that exposed surfaces of the hollow
spheres are primarily the {222} plane with a d-spacing of
+
The morphological evolution of these YMSHs was inten-
sively investigated as follows. From the thermogravimetric anal-
ysis (TGA) curve (Figure S4, Supporting Information), starting
at 100 °C (I), the curves show a slight decline, which is due
to the evaporation of water. From 200 to 550 °C (II), the curve
presents a linear decline, which is attributed to the thermal
decomposition of organics and combustion of the carbon com-
ponents, during which the material loses 84% of its mass. After
reaching 550 °C, the curve is flat, indicating that steady-state
YMSHs were obtained. A TEM was employed to monitor the
morphological evolution of the pre-YMSH materials during
the annealing process, and the entire formation process is
illustrated in Figure 2a. The pre-YMSH materials with highly
smooth surfaces are shown in Figure 2b. Meanwhile, X-ray
photoelectron spectroscopy (XPS) measurements were also
conducted to explore the composition of the pre-YMSH mate-
rials, as illustrated in Figure S5a–c (Supporting Information).
The peaks of the C 1s region are shown in Figure S5a (Sup-
porting Information), and those at 284.5, 285.2, 286.3, and
288 eV are attributed to the CC, CN, CO, and CO bonds,
respectively. The OH bond (533.3 eV), CO bond (532.5 eV),
and CO bond (531.3 eV) can be observed in the characteristic
peaks of the O 1s region (Figure S5b, Supporting Information).
The two kinds of Y 3d peaks, located at 158.5 and 156.4 eV, cor-
respond to Y 3d3/2 and 3d5/2 of Y O , respectively, and a sec-
0
.307 nm, which agrees well with the XRD pattern. The diffrac-
tion rings of the selected area electron diffraction (SAED) indi-
cate the polycrystalline characteristics of the material, which
was further in agreement with the XRD results (Figure 1f). The
hollow structures of the hierarchical multishelled yttrium-oxide
material are further studied by high-angle annular dark-field
scanning transmission electron microscopy (HAADFSTEM)
mapping, as presented in Figure 1g, indicating that the multi-
shelled yttrium-oxide structures are uniform and hollow, which is
consistent with the above results. The formation of multishelled
hollow spherical structures was further investigated by adjusting
the quantities of YCl ꢀ•ꢀ6H O, urea, and glucose in the reac-
3
2
tion (Figures S2 and S3, Supporting Information). Multishelled
hollow spherical structures were first obtained at 0.12 m glucose,
as the mass of glucose increased from 0 to 0.18 m in the mixed
solution with urea and YCl (Figure S2, Supporting Information).
3
It has been reported that monodisperse carbon microspheres can
be prepared from glucose solutions by the hydrothermal method.
After absorbing metal ions, the carbon microspheres act as sac-
rificial templates to generate metal oxide multishelled hollow
[
53–56]
structures after annealing at 550 °C in air.
Here, we used a
one-step hydrothermal method to produce carbon microspheres
containing yttrium (Y ) ions by introducing urea as a competing
coordination agent. Without urea, the coordination of the Y3 ions
2
3
3+
ondary doublet peak located at 160.3 and 158.3 eV was found in
the Y 3d region (Figure S5d, Supporting Information), which
+
Figure 2. a) Schematic illustration of the formation mechanism of the YMSHs. b–f) TEM images of pre-YMSHs and the obtained product by annealing
at 550 °C for different durations: 0, 0.5, 1, 4, and 6 h. All scale bars are 500 nm.
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is consistent with previous reports.[57] The composition of the
pre-YMSH materials was further confirmed by FTIR spectros-
copy. The results are shown in Figure S5d (Supporting Infor-
A YMSH-based CTL sensor was fabricated to detect the ana-
lytes. The luminescence signal is generated and emitted due to
the relaxation of excited products from their electronic excited
−1
mation). The stretching vibration at 1150 cm in the region of
state to the ground state during the catalytic oxidation reac-
−
1
[58–62]
1
300–1000 cm corresponds to the OH group, and the vibra-
tion of the analyte molecule on the surface of YMSHs.
As
−1
tion bands at 1630 and 1650 cm correspond to the CC and
CO groups, respectively. The NH asymmetric stretching at
reported in the literature, the luminescent intensity and signal-
to-noise ratio (S/N) of the CTL response are strongly dependent
on the detection wavelength, operating temperature, and flow
−
1
3
436 cm was attributed to the NH of urea. Hence, amor-
[
58–62]
phous pre-YMSH solid spheres are formed from yttrium ions,
urea, and glucose. The color of the obtained core–shell struc-
tured sample with rough surfaces changes from deeply brown
to black after annealing at 550 °C for 0.5 h (Figure 2c). How-
ever, because the annealing time (0.5 h) is short, the core–
shell structure is not apparent. The HAADF-STEM and ele-
mental mapping images of the pre-YMSH solid spheres after
annealing at 550 °C for 0.5 h illustrate that amounts of the
C, N, and O elements on the surface of the pre-YMSH solid
spheres are reduced and these elements form particles during
the annealing process (Figure S6, Supporting Information). As
the annealing step is extended to 1 h, yolk–shell structures with
a pre-YMSH core and a Y O shell are observed as an interme-
rate.
The sensor response to 18 ppm methanol was tested
through a series of interference (bandpass) filters in the range
400–640 nm to obtain the optimal wavelength (Figure S7, Sup-
porting Information). With increasing wavelength, both the
intensity and S/N reached a maximum at 490 nm and then
decreased. Thus, 490 nm was regarded as the optimal wave-
length for the following experiments. The response of the
sensor toward different operating temperatures and flow rates
was also investigated, as shown in Figures S8 and S9 (Sup-
porting Information). The optimal temperature and flow rate
−
1
were 100 °C and 240 mL min , respectively, for the detection
of methanol in the subsequent studies. Under the selected con-
ditions described above, the CTL response profile of methanol
on the YMSHs is evaluated by the sensor response and recovery
times for three different concentrations of methanol vapor.
The CTL intensity increased as the concentration of methanol
vapor increased, while the response and recovery times were
less than 10 and 60 s, respectively (Figure 3a). Figure 3b shows
the reproducibility of the responses of the CTL sensor toward
2
3
diate product, as seen in Figure 2d. When further extending
the annealing process, an obvious yolk–shell structure with a
small solid core and two well-defined shells is seen (Figure 2e).
Figure 2f shows that homogeneous YMSHs, as a unique 3D
hierarchical structure, was successfully obtained after further
extending the reaction time to 6 h.
Figure 3. a) CTL spectra of the response and recovery times at different methanol concentrations, b) the reproducibility of the CTL response signals
for methanol over a series of different concentrations ranging from 0.36 to 90 ppm, c) linear range of the calibration curves of the YMSHs, and d) the
selectivity toward methanol of the methanol CTL gas sensor based on YMSHs. Conditions are wavelength: 490 nm, temperature: 100 °C, flow rate of
−
1
the carrier gas: 240 mL min .
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methanol for a series of different concentrations ranging from
To verify the impact of the 3D hierarchical structure of the
YMSHs, commercially available solid Y O nanoparticles (NPs)
0
0
.36 to 90 ppm. A linear calibration curve over the range of
.36–90 ppm was obtained, and the linear regression equa-
2
3
were used in a methanol CTL sensor for comparison, which
was shown to exhibit poor sensitivity and selectivity for meth-
anol detection under the same testing conditions (Figure S11,
Supporting Information). Figure S12 (Supporting Information)
shows the Brunauer–Emmett–Teller (BET) N2 adsorption–
desorption measurement results of the YMSHs and commercial
Y O nanoparticles. The YMSHs show a high specific surface
tion is I = 23119.67 + 3577.77 C, where the limit of detection
is 71 ppb (S/N = 3), the correlation coefficient (R) is 0.9985, I is
the average CTL intensity, and C is the concentration of meth-
anol (Figure 3c). In addition, the CTL intensities at 18 ppm
of methanol were recorded every 2 h over 7 d during the cata-
lytic oxidation on the YMSHs. The results show no significant
changes over time, which indicates a relatively long lifetime for
the sensor (Figure S10, Supporting Information). Meanwhile,
YMSHs were found to show an excellent selectivity toward
methanol by investigating the sensor response to coexisting
foreign substances, including formaldehyde, ethanol, benzene,
n-hexane, formic acid, toluene, cyclohexane, trichloromethane,
and ammonia, under the same concentrations and test condi-
tions. As shown in Figure 3d, there is either no response or
a weak response when a foreign volatile organic compound
2
3
2
−1
area of 71.2 m g due to their unique multishelled structure,
which is significantly higher than that of commercial Y O nan-
2
3
2
−1
oparticles at 6.3 m g . The specific multishelled structures of
the YMSHs offer a large active surface area that results in an
enhancement of the CTL response because they exhibit more
crystal facets that possess the desired active sites for the adsorp-
tion of methanol. Meanwhile, the porous hierarchical structures
are favorable for the diffusion of the detected gas into/out of
the sensor shells, which can also improve the response charac-
teristics. Notably, the high-resolution TEM (HRTEM) image of
the commercial solid Y O NPs (Figure S13,
(VOC) is passed through the sensor.
2
3
Supporting Information) shows a mixture of
exposed facets, including the {222}, {440},
and {400} facets. The XRD pattern results
reveal that the ratio of the exposed {222}
and {440} facets of the YMSHs is ≈1.8 times
higher than that of the commercial Y O
2
3
NPs, which indicates that the {222} facet
may directly correlate with the sensitivity and
selectivity of the Y O materials (Figure S14,
2
3
Supporting Information). To confirm the
above deduction, density functional theory
(
DFT) calculations were conducted to explore
the methanol detection abilities of Y O , and
2
3
all the detailed computational parameters
can be found in the Supporting Information.
We first studied the adsorption properties of
methanol and the other coexisting foreign
substances on the (222) plane of Y O , and
2
3
the calculated adsorption configurations as
well as the adsorption energies are shown
in Figure 4. No obvious changes in molec-
ular structure were observed after the meth-
anol molecule or the other substances were
adsorbed onto the Y O substrate, and all the
2
3
Eads values were less than 1.5 eV. Therefore,
it can be proven that all the substances can
be physically adsorbed. The Eads for methanol
is the most negative, at −1.02 eV, among all
the substances, which means that the {222}
facets greatly benefit the adsorption of meth-
anol and the subsequent catalysis compared
with the benefits to the other substances.
The similar adsorption energies for methanol
and the other coexisting foreign substances
on the (440) plane of Y O , by the DFT cal-
2
3
Figure 4. Theoretical simulation of the VOC adsorption ability of the YMSHs. a) Optimized
adsorption structures of the geometric binding configurations and binding energies of the
VOCs with the (222) plane of Y O . b) The adsorption energies and structures of different
culations, indicate that the {222} facet of
Y O presents a higher selectivity than does
2
3
2
3
the {440} facet (Figure S15, Supporting
Information), which can explain the high
gasses on the Y O surface. The gray, red, blue, and white balls denote C, O, N, and H atoms,
2
3
respectively. A lower adsorption energy (further from zero) denotes a stronger adsorption.
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methanol detection performance of the multishelled structures
of Y O compared with that of the commercial solid Y O NPs.
2
3
2
3
Moreover, single-shell Y O hollow spheres were used in the
2
3
methanol CTL sensor for comparison (Figure S16, Supporting
Information), and they exhibited a lower relative CTL intensity
than did the multishelled Y O hollow spheres under the same
2
3
testing conditions (Table S1, Supporting Information). There-
fore, benefiting from the synergistic effects of a multishelled
hollow structure with a large surface area and exposed {222}
crystal facets, the sensor based on YMSHs shows a high selec-
tivity and ultrasensitivity toward methanol, which is confirmed
by the consistent experimental and simulated results.
The catalytic mechanism of methanol oxidation on the sur-
face of the YMSHs was investigated to evaluate the correlation
between the catalytic activity and CTL response. According to
literature reports, there are many kinds of oxidative products
from methanol, such as HCHO, CO, and CO2.[ The energy
changes for the various oxidative products of methanol have
been illustrated as follows
63]
Figure 5. Schematic illustration of the configuration of the CTL system
for the identification of methanol by the CTL reaction on YMSHs.
CH
3
OH+1/2O
2
→ H
2
2
CO+H O
mixed methanol and ethanol solutions is still in high demand.
Herein, an aqueous mixture comprising 0.23 µL (18 ppm) of
methanol, 6 mL of ethanol, and 4 mL of water was examined.
A CaO tube was connected to the front end of the inlet of a
quartz tube, which was used to remove water from the aqueous
mixture during the detection test. Therefore, detection could
proceed immediately after the removal of water. The analysis
results show that there is 17.5 ppm of methanol in the mixture,
which indicates these materials have great potential in the field
of wine inspection.
(1)
(2)
(3)
−1
∆H = −159 kJ mol
CH
3
OH+O
2
2
→ CO+2H O
−1
∆H = −389 kJ mol
CH
3
OH+3/2O
2
→ CO
2
2
+2H O
−1
∆H = −674 kJ mol
From the above chemical equations, it can be easily deduced that
CO is the final product of methanol oxidation since it has the
2
maximum enthalpy change for the oxidation reaction. Here, the
catalytic reaction final products of methanol on the surface of
YMSHs were monitored by in situ FTIR characterization tech-
niques. A new absorbance feature at 2350 cm−1 was observed
after injecting 18 ppm of methanol, as seen in Figure S17
3
. Conclusion
In conclusion, we have developed a simple and low-cost sensor
based on 3D hierarchical Y O multishelled hollow structures
2
3
(
Supporting Information), which is ascribed to the generation
to detect methanol with high selectivity and ultrasensitivity
(low limit of detection: 71 ppb). The unique hierarchical mul-
tishelled hollow structures have a large surface area and abun-
dance of {222} facets, which contribute to the high selectivity
and ultrasensitive detection of methanol and is confirmed
by the consistent experimental and simulated results. The in
situ FTIR spectral analysis results indicate that the YMSHs
demonstrate the highest catalytic activity toward methanol
oxidation, which further verifies the high methanol detection
performance of the hierarchical multishelled Y O structures.
More interestingly, a sensor with a simple CaO apparatus can
be applied to detect methanol in a liquid sample mixture of
ethanol, methanol, and water, which represents a unique and
strong ability to distinguish methanol. This simple method for
detecting methanol can open the way to economical applica-
tions in environmental monitoring and food safety, including
wine safety inspections.
of CO in the products. This result indicates that YMSHs dem-
2
onstrate the highest catalytic activity for methanol oxidation,
which further verifies the high methanol detection perfor-
mance of these multishelled structures of Y O . A schematic
illustration of the CTL configuration system for the identifica-
tion of the methanol CTL reaction on the surface of the YMSHs
is shown in Figure 5.
To further demonstrate the excellent selectivity of the
YMSHs toward the detection of methanol, two groups of
mixed gas (first group: 18 ppm methanol, 18 ppm ammonia,
and 18 ppm formaldehyde; second group: 18 ppm methanol,
2
3
2
3
1
8 ppm ammonia, and 18 ppm benzene) were analyzed using
the YMSH sensor (see Table S2, Supporting Information).
According to the calibration curve of the CTL signal inten-
sity versus concentration, 18.8 and 18.3 ppm of the analyte
were detected, respectively. The relative standard deviation
(RSD) of the CTL intensity is less than 3%, which represents
a unique and high ability to distinguish methanol. Interest-
ingly, our device is not only applicable to gas samples but is 4. Experimental Section
also suitable for liquid samples. It is well known that wines
unavoidably contain low concentrations of methanol, and a reli-
able methanol sensor that can selectively detect methanol in
Synthesis of Yttrium Oxide Multishelled Hollow Structures: The YMSHs
were prepared by a typical synthesis. A mixture of 6 mL of a 0.5 m urea
−
3
solution and 6 mL of a 0.2 × 10 m YCl · 6H O solution was slowly
3
2
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added to 20 mL of 0.5 m glucose to form a homogeneous solution
under vigorous stirring for 30 min. Then, the homogeneous solution
was transferred to and sealed in a Teflon-lined autoclave and reacted
at 160 °C for 24 h. Subsequently, after cooling to room temperature,
the dark brown products were centrifuged and washed with additional
deionized water several times before being placed in an oven to be
dried at 60 °C for 12 h. Finally, the solid powder was calcined in a muffle
furnace under air atmosphere at 550 °C for 360 min.
Acknowledgements
This work was supported by National Key R&D Program of China
(International Collaboration program) granted by Chinese Ministry of
Science and Technology (2016YFE0129800) and the National Natural
Science Foundation of China (21822202 and 21507054). This project
was supported by the Special Scientific Research Fund of the National
General Administration of Quality Supervision in China (2018IK027).
This was also a project supported by the Natural Science Foundation
of Jiangsu Province (BK20150007), project funded by 111 project, Joint
International Research Laboratory of Carbon-Based Functional Materials
and Devices, Collaborative Innovation Center of Suzhou Nano Science
& Technology, and the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD). The authors acknowledge
Prof. Mingwang Shao for discussing the results about structure
characterization.
Sensor Fabrication: The CTL detection system was similar to that of
[
64]
a previous work.
Briefly, the present CTL sensor comprised three
major parts: a laboratory-made reaction cell, a digital temperature
controller (Chao Yang Automation Instrumentation Co., Ltd., Beijing,
China), and a computerized BPCL ultraweak luminescent analyzer
(Biophysics Institute of the Chinese Academy of Science, Beijing, China)
equipped with a CR-105 photomultiplier tube (PMT, Model GDB23,
Beijing Nuclear Instrument Factory, Beijing, China). The reaction cell
was fabricated by placing a 4 mm diameter cylindrical ceramic heater
(
Ningbo Electric Iron Factory, Ningbo, China) in the middle of a 10 mL
quartz tube equipped with a gas inlet and outlet. YMSH catalyst (0.4 g)
was coated around the ceramic heater after the surface of the ceramic
heater was brushed with glue (≈0.1 mL). The targeted temperature of the
ceramic heater was controlled by a digital temperature controller, and
then the ceramic heater with the YMSH catalyst was heated (500 °C, 3 h)
to avoid the effects of previous absorbates at the beginning of the
experiment. The CaO tube was arranged on the front end of the inlet
of the quartz tube, which was used to remove water from the aqueous
mixture during the detection test. Valve switches were installed at both
the inlet and the outlet to allow the reaction cell to be opened (when the
system was in the airstream flow reaction cell mode) or closed (when
the system was in the closed reaction cell mode). A photomultiplier tube
was used to detect and record the CTL signal produced by the catalytic
reaction. The detection wavelengths were in the range of 400–640 nm,
which could be selected for by changing the interference optical filters,
which had a bandwidth of 24 nm (Institute of Biophysics, Academia
Sinica, Beijing, China).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
cataluminescence, methanol, multishelled hollow structure, volatile
organic compounds, yttrium oxide
Received: November 9, 2018
Revised: December 19, 2018
Published online:
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