Nasim Jafari1, Sedigheh Zeinali1. 1. Department of Nanochemical Engineering, School of Advanced Technologies, Shiraz University, Shiraz 7193615511, Iran.
Abstract
Formaldehyde is a volatile organic compound (VOC) with extensive applications, volatility, and toxicity, which have made it an important risk to human health even at low concentrations. Therefore, rapid detection of formaldehyde vapors in the environment is a necessity. Herein, we introduce a resistive gas sensor based on zeolitic imidazolate framework-8/multiwalled carbon nanotube (ZIF-8/MWCNT) for detection of formaldehyde vapors at room temperature. In this sensor, a low amount of MWCNTs was used in order to improve the electrical conductivity of the porous nanoparticles of ZIF-8. The sensor was fabricated by deposition of a thin layer of the nanocomposite onto interdigitated electrodes, and its sensing ability was investigated on exposure to formaldehyde vapors. The obtained sensor showed sensitive and fast responses to different concentrations of formaldehyde, and the sensor response to formaldehyde was higher than toward some other VOCs, including methanol, ethanol, acetone, and acetonitrile. Furthermore, because of the hydrophobic nature of ZIF-8, the effect of relative humidity on the gas-sensing performance was insignificant, which proves that this sensor is suitable for use under humid conditions.
Formaldehyde is a volatile organiccompound (VOC) with extensive applications, volatility, and toxicity, which have made it an important risk to human health even at low concentrations. Therefore, rapid detection of formaldehyde vapors in the environment is a necessity. Herein, we introduce a resistive gas sensor based on zeolitic imidazolate framework-8/multiwalled carbon nanotube (ZIF-8/MWCNT) for detection of formaldehyde vapors at room temperature. In this sensor, a low amount of MWCNTs was used in order to improve the electrical conductivity of the porous nanoparticles of ZIF-8. The sensor was fabricated by deposition of a thin layer of the nanocomposite onto interdigitated electrodes, and its sensing ability was investigated on exposure to formaldehyde vapors. The obtained sensor showed sensitive and fast responses to different concentrations of formaldehyde, and the sensor response to formaldehyde was higher than toward some other VOCs, including methanol, ethanol, acetone, and acetonitrile. Furthermore, because of the hydrophobic nature of ZIF-8, the effect of relative humidity on the gas-sensing performance was insignificant, which proves that this sensor is suitable for use under humid conditions.
Formaldehyde or methanal
(CH2O) is a colorless, strong-smelling
volatile organiccompound (VOC), which is an important precursor for
many chemicals. Formaldehyde is one of the major causes of sick building
syndrome, a situation in which occupants of a building may encounter
health problems including eye irritation, cough, headache, nausea,
and respiratory issues. These problems are mostly created by the sources
inside the building, including building materials, some wooden materials,
adhesives, resins, insulation materials, and carpeting and cleaning
agents.[1,2] Outdoor sources of formaldehyde include
exhaust gases of motor vehicles, flue gases from heating facilities,
and incinerators. There are also some natural sources of formaldehyde
emission, such as photochemical oxidation and incomplete combustion
of hydrocarbons.[3] In addition, formaldehyde
is known as a humancarcinogen on long exposures, and because of its
extensive applications, volatility, and toxicity, it is an important
risk to human health. Therefore, quick detection of formaldehyde is
very important and necessitates the use of gas sensors.Gas
sensors are widely used in the industries for detection of
toxic or explosive gases, air quality monitoring, medical diagnostics,
and food quality control.[4] Among different
gas sensors, those that work at low temperatures are more desirable
because they consume lower energy, have a simpler system, and so are
not expensive. In addition, in the case of detection of explosive
gases, high operating temperature sensors may bring the risk of ignition
or explosion. Moreover working at high temperatures may reduce the
lifetime of sensors.[5]Resistive sensors
are one of the most desirable sensors, mostly
because of a noncomplicated and low-cost system that can be assembled
in a small and portable setup.[5] In these
sensors, gas adsorption on an adsorbent material causes changes in
the electrical resistance of the material. For this purpose, the adsorbent
needs to be a semiconducting material for being able to make electrical
signals.[6]One of the widely used
sensing materials in resistive gas sensors
are metal-oxide sensors which are known for their high sensitivity;
however, they have low selectivity and low surface area, and they
work at high temperatures because of their purely inorganic structure.[4,7] Therefore, porous sensing materials with more surface area and lower
operating temperature are more desirable; this includes metal organic
frameworks (MOFs). MOFs are constructed from metal ions or clusters
coordinated to organic ligands and possess remarkable properties such
as a high specific surface area, a hybrid organic–inorganic
structure, and tunable porosities,[8,9] which make
them ideal for gas sensing.Zeolitic imidazolate framework-8
(ZIF-8) is a kind of MOF in which
divalent zinccations are linked through 2-methylimidazole (Hmim)
linkers and is reported to show high crystallinity, nanoporous structure,
large surface area, high chemical and thermal stabilities, and hydrophobicity.[10,11] ZIF-8 is considered as a high-performance sensing material in many
types of gas sensors, such as optical sensors,[12−15] quartz crystal microbalance sensors,[16] microcantilever devices,[17] and other sensors for detection of different gases and
VOCs. However, till date there are few reports of ZIF-8 as a sensing
material in resistive gas sensors because of the poor electrical conductivity
of this material. In most of the reports, ZIF-8 was used in the ZnO@ZIF-8core–shell structure in which ZIF-8 improved the selectivity
of the semiconducting ZnO gas sensor; however, these sensors work
at high temperatures. For example, Tian et al. used this structure
to detect formaldehyde at 300 °C,[18] and Drobek et al. did the same work for sensing hydrogen with improved
selectivity.[19] Also, Matatagui et al. have
used ZIF-8 in a composite with ZIF-67 in a resistive sensor to improve
the response of ZIF-67 sensor to hydrogen and toluene at the temperature
of 180 °C.[20]Furthermore, in
the case of formaldehyde, some works have been
done which report detection of different concentrations of formaldehyde
by resistive sensors. For example, Jia et al. fabricated a formaldehyde
sensor by ZnSnO3, which could detect formaldehyde at a
concentration range of 5–100 ppm; however, the working temperature
for this sensor was higher than 200 °C.[21] In addition, Chimowa et al. tested encapsulated zinc, zinc oxide,
and iodine within double-walled carbon nanotubes (CNTs) for detection
of various mass concentrations of formaldehyde ranging from 1.8 to
4%.[22]In this research, we selected
ZIF-8 as an acceptable sensing material
for sensing formaldehyde based on the literature. However, it should
be used in a composite form with some conductive or semiconductive
material. For this purpose, in the present work, ZIF-8 was combined
with functionalized multiwalled CNTs (MWCNTs) to compensate for its
low conductivity and to be able to work as a sensing material for
a resistive gas sensor at room temperature.
Materials and Methods
Materials
All of the chemicals including Hmim (C4H6N2), zinc nitrate hexahydrate [Zn(NO3)2·6H2O], methanol (99.9%), formaldehyde
(CH2O, 37% aqueous solution), ethanol (99.9%), acetone
(99.9%), and acetonitrile (99.9%) were purchased from Merck Company
and used without further purifications. MWCNT (8–15 nm outer
diameter, 50 μm length and purity > 95%) was purchased from
Neutrino Company (Iran). A custom-made polymer substrate with an interdigitated
electrode (IDE) was used as the substrate for fabrication of the sensing
layer and consisted of 38 silver fingers with 150 μm distance
between each pair. Ag paste was purchased from Hezareh 3 Company (Iran)
and used to connect the wires to sensor electrodes.
Characterization
Instruments
X-ray diffraction (XRD)
patterns of samples were collected by a Bruker D8 Advance X-ray diffractometer
with Cu Kα radiation (λ = 0.15418 nm) in the 2θ
range of 5–80°. The morphology was investigated by scanning
electron microscopy (SEM) images which were taken by a TESCAN VEGA3
microscope. Fourier transform infrared (FTIR) spectra were collected
using a PerkinElmer Spectrum RXI FTIR spectrometer to investigate
chemical bonds. N2 adsorption/desorption isotherms of samples
were measured by a Micromeritics ASAP 2020 instrument at 77 K. The
specific surface area of samples was calculated by the Brunauer–Emmett–Teller
(BET) and Langmuir methods, and the t-plot pore volume
was calculated for evaluating the micropore volume.
Synthesis of
ZIF-8 Nanoparticles
ZIF-8 was synthesized
according to a reported procedure with some modifications.[23] Zinc nitrate hexahydrate (0.5 g) was dissolved
in 5 mL of deionized water and 20 mL of methanol, and 1.5 g of Hmim
was dissolved in 25 mL of methanol. The solutions were mixed together
rapidly, and the obtained milky suspension was stirred at room temperature
for 16 h, until the suspension got white color. The final solution
was centrifuged to separate the precipitated ZIF-8 solids, washed
several times with deionized water and methanol, and kept in methanol
for 1 day to bring unreacted precursors out. Finally, the precipitates
were centrifuged again and dried at 60 °C overnight to yield
white fine powders of ZIF-8.
Carboxyl Functionalization of MWCNTs
Commercial CNTs
are supplied in the form of heavily entangled bundles, and their dispersion
in the solvent is not satisfying. Furthermore, the interactions between
CNTs and the composite matrix are poor;[24] so CNTs need to be functionalized before compositing. For this purpose,
these particles were carboxyl-functionalized for better distribution
in the composite. MWCNTs (40 mg) were added to 100 mL of H2SO4/HNO3 (1:3 volume ratio) solution and were
stirred at 120 °C under reflux for 12 h. The obtained MWCNTs
were washed with water several times and dried at 60 °C.[25]
Preparation of ZIF-8/MWCNT Nanocomposite
For preparing
the ZIF-8/MWCNT nanocomposite, “ex situ synthetic approach”
was selected which is a typical method for the synthesis of MOF/carboncomposites.[26] According to this method,
MWCNTs were directly mixed with presynthesized ZIF-8 and ethanol as
the solvent. Different combinations of ZIF-8 and MWCNTs were tested,
and finally, the suspension with 2.5% wt of MWCNTs was found to be
the best one. For this purpose, 1 mg of MWCNTs and 39 mg of ZIF-8
were separately dispersed in 10 mL of ethanol in an ultrasonic bath
for 30 min and then mixed together and stirred for 24 h. The final
suspension was sonicated and heated slightly to lose the solvent without
missing the homogeneity, until the solution volume reached 2 mL.
Preparation of Sensing Layer
The prepared composite
was deposited on top of the IDEs with the drop-casting method. For
making a uniform film, the homogeneity of the prepared composite suspension
is important, so it should be sonicated well before deposition. After
drop-casting onto the IDE substrate, it was kept in the oven for 1
h at 60 °C. In this step, high evaporation rates should be avoided
to prevent crack formations on the final film. Finally, two pieces
of copper wire were connected to the electrodes by silver paste, and
they were kept in 100 °C for 1 h until the paste was dried completely
(Figure ).
Figure 1
Silver IDEs
(a) before the composite deposition and (b) after the
composite deposition.
SilverIDEs
(a) before the composite deposition and (b) after the
composite deposition.The observed resistance
of this layer was about 120 kΩ at
room temperature (25–27 °C) which was acceptable for the
purpose of this report.
Gas-Sensing Procedure
A home-made
sensor apparatus
was used for testing of the fabricated sensor which included a well-sealed
Teflon/Pyrex chamber (3.7 L volume) (Figure ). The fabricated sensor was located in the
testing chamber, and while the chamber lid was closed, specified amounts
of liquid VOCs were imported through Agilent GC syringes (1 or 10
μL) onto top of a heater. For each VOC, the temperature of the
heater was set at its boiling point, so the VOCs were evaporated immediately
after reaching the heater surface. Resistance of the sensing layer
was measured by a digital multimeter (Hioki DT4252). In order to make
a homogeneous concentration of vapors in the chamber, a fan was installed
inside the chamber. Also, the chamber was equipped with a humidity
sensor, which showed the relative humidity (RH) inside the container
during the sensing process. All of the experiments were performed
at room temperature, and the temperature was monitored by a thermometer
placed into the chamber.
Figure 2
Gas sensor testing apparatus.
Gas sensor testing apparatus.The main analyte in this report was formaldehyde, and other
VOCs
including methanol, ethanol, acetone, and acetonitrile were analyzed
for comparison. After injection of different amounts of these VOCs,
resistance of the sensing material increased instantly. The resistance
changes were recorded during the time until it reached an equilibrium.
Then, the gas molecules were released by introducing fresh air into
the chamber. Every test was repeated three times for investigating
the repeatability of the sensor. Furthermore, formaldehyde sensing
experiment was performed under different humidity conditions to examine
the effect of humidity on the sensor performance. For other experiments,
the RH of the chamber was 18–20%, and the air temperature was
25–27 °C.
Results and Discussion
Characterization of Prepared
Materials
The structures
of synthesized ZIF-8, functionalized MWCNTs, and ZIF-8/MWCNTcomposite
were characterized by XRD analysis (Figure ). The pattern of ZIF-8 is in perfect agreement
with the literature.[27,28] The sample has pure phase of
ZIF-8, and predominant peaks at 2θ = 7.44, 10.43, 12.79, 14.81,
16.50, 18.13, 22.19, 24.62, 26.79, 29.77, 30.71, 31.59, and 32.47°
are attributed to the (110), (200), (211), (220), (310), (222), (411),
(332), (422), (431), (440), (433), (442), and (532) planes, respectively.[27] In addition, the sharpness and narrowness of
the peaks prove the high crystallinity of the structure. The comparison
between ZIF-8 in pure form and composite form indicates that a combination
of MWCNTs with ZIF-8 had no significant effect on the XRD pattern
of this material. As it is evident in the inset of Figure , MWCNT has only one weak peak
around 2θ = 25.75°, which is ignorable compared to strong
peaks of ZIF-8. Also, the concentration of MWCNTs in the composite
form is too low to make change in the XRD pattern of ZIF-8.
Figure 3
XRD patterns
of ZIF-8 and ZIF-8/MWCNT nanocomposite. The inset
graph shows the XRD pattern of functionalized MWCNTs.
XRD patterns
of ZIF-8 and ZIF-8/MWCNT nanocomposite. The inset
graph shows the XRD pattern of functionalized MWCNTs.The morphologies of ZIF-8 and ZIF-8/MWCNT are investigated
by SEM
images. Figure a shows
the uniform crystals of ZIF-8 with sharp facets, which have a particle
size in the range of 80–120 nm. The crystals have a rhombic
dodecahedral morphology that is a typical shape for ZIF-8, which has
12 exposed (110) faces. This claim is proved by the XRD pattern of
ZIF-8 in which the sharpest peak is related to the mentioned structure.[27]Figure b shows the MWCNT/ZIF-8composite in which the existence of
MWCNT strands among ZIF-8crystals can be observed. These strands
link the crystals to each other and make paths for electron transfer,
which gives the semiconductivity feature to the composite. MWCNTs
are hardly seen in the mixture, first because the amount of these
materials is lower than ZIF-8crystals. Another reason is that carboxyl-functionalized
MWCNTs had interaction with Zn2+ of ZIF-8[23] and are covered with these crystals, so MWCNTs are not
so clear in the SEM image.
Figure 4
SEM images of (a) ZIF-8 and (b) ZIF-8/MWCNT
nanocomposite.
SEM images of (a) ZIF-8 and (b) ZIF-8/MWCNT
nanocomposite.For investigating the chemical
bond vibrations of ZIF-8 and ZIF-8/MWCNT,
FTIR spectra of the sample were studied in the range of 4000–400
cm–1 (Figure ). ZIF-8 spectra is in good agreement with the literature.[29] The bands at 3133 and 2928 cm–1 are attributed to the aromatic and aliphaticC–H stretches
of the imidazole ring, respectively. The peak at 1587 cm–1 can be associated with the C=N stretch mode. The intense
bands at 1350–1500 cm–1 can be referred to
the entire ring stretching and the bands in the region of 900–1350
cm–1 are for the in-plane bending of the ring, whereas
those between 600 and 800 cm–1 are associated with
out-of-plane bending. The band at 419 cm–1 exhibits
the Zn–N stretch mode and shows that Zncations are connected
to nitrogen atoms of Hmim successfully.[29]
Figure 5
FTIR
spectra of ZIF-8, COOH-functionalized MWCNTs, and ZIF-8/MWCNT
nanocomposite.
FTIR
spectra of ZIF-8, COOH-functionalized MWCNTs, and ZIF-8/MWCNT
nanocomposite.FTIR spectra of acid-functionalized
MWCNTs shows a broad peak at
3421 cm–1, which is associated with the O–H
stretch of carboxylic groups. The peak at 1730 cm–1 is attributed to the C=O stretch mode of carboxylic groups
and indicates that MWCNTs are successfully functionalized. Also, the
C–O stretch mode appeared at 1283 cm–1, and
the peak at 1638 cm–1 indicates aromaticC=C
groups.[30,31]In the composite form, all of the
ZIF-8 peaks can be seen and no
significant change is observed because of the low concentration of
MWCNTs in the composite. However, the peak of 1738 cm–1 in the composite form can be associated with the C=O stretch
mode of the carboxylic group of MWCNTs. Also, the broad peak of O–H
stretch in 3448 cm–1, which is intensified in the
composite in comparison to pure ZIF-8, is another sign of the presence
of MWCNTs in the composite.The porous structure of evacuated
ZIF-8 and ZIF-8/MWCNTcomposite
was evaluated by N2 adsorption and desorption in the range
of p/p0 = 0.01–0.99.
According to the IUPACclassifications,[32] a combination of type I and type IV isotherm behaviors was observed
for both samples with a small hysteresis loop at relatively high pressures
(Figure ), which reveals
the dominance of microporous nature with minor mesopores. At the same
pressure, the composite exhibits lower N2 adsorbed quantity
than pure ZIF-8 as a consequence of some probable aggregations in
the composite and blocking of pore openings of ZIF-8crystals because
of MWCNT presence.
Figure 6
Nitrogen adsorption/desorption of (a) ZIF-8 and (b) ZIF-8/MWCNT
nanocomposite at 77 K.
Nitrogen adsorption/desorption of (a) ZIF-8 and (b) ZIF-8/MWCNT
nanocomposite at 77 K.The Langmuir surface
area, BET surface area, total pore volume, t-plot
micropore volume, and average pore width for ZIF-8
and ZIF-8/MWCNTcomposite are calculated by using the obtained data
and are summarized in Table . For synthesized ZIF-8, as shown in Table , the BET surface area is 1483.13 m2/g which is higher than the report with a similar synthesis method.[23] It might be due to remaining unreacted precursors
in cavities which common washing or heating is unable to bring out;
so in this work, an extra washing step was added by keeping the particles
in methanol for 1 day. The BET surface area of 1412.76 m2/g was obtained for the ZIF-8/MWCNTs nanocomposite, which is a little
lower than for the pure ZIF-8. This decrease in the internal surface
area is expectable because of MWCNT presence. However, this decrease
is not so significant and has a negligible effect on the performance
of the ZIF-8/MWCNT nanocomposite as a highly porous sensing material.
Also, according to the results shown in Table , the average pore sizes of ZIF-8 and ZIF-8/MWCNT
are about 2.4 and 2.3 nm respectively, which confirm the isotherm
types mentioned above.
Table 1
Textile Properties
of ZIF-8 and ZIF-8/MWCNT
Langmuir
surface area (m2/g)
BET surface
area (m2/g)
total pore
volume at p/p0 = 0.97 (cm3/g)
t-plot micropore volume (cm3/g)
average pore
width (4V/A by BET) (Å)
ZIF-8
1961.86
1483.14
0.91
0.64
24.51
ZIF-8/MWCNT
1861.62
1412.76
0.82
0.61
23.25
Sensor Performance Parameters
To verify the performance
of the sensor, the response of the sensor was measured on exposure
to different concentrations of formaldehyde (5–100 ppm). Injection
of analyte and adsorption of gas molecules onto the surface and pores
of the nanocomposite caused an increase in the electrical resistance
of the sensing material. Figure shows the response–recovery cyclic diagram
of the sensor on exposure to different formaldehydeconcentrations
at room temperature. The separated diagram for each concentration
is shown in Figure S1. As is evident, the
sensor shows high response to formaldehyde. In addition, this sensor
was able to detect a trace amount of formaldehyde as low as 5 ppm.
This considerable response even at low concentrations can be related
to the high surface area and the microporous structure of the ZIF-8
material.
Figure 7
Response–recovery cycles of the sensor on exposure to 5–100
ppm of formaldehyde (at 25–27 °C and 18–20% RH).
Response–recovery cycles of the sensor on exposure to 5–100
ppm of formaldehyde (at 25–27 °C and 18–20% RH).Because formaldehyde is a reductive gas and can
cause an increase
in resistivity (or reduction of conductivity) of the sensor, it can
be concluded that the obtained composite is a p-type semiconductor.[5] Formaldehyde decreases the conductivity by donating
electrons to the valence band of the sensing material, which decreases
the number of holes and increases the separation between the Fermi
level and the valence band. This increases the resistance of the material,
which is illustrated in Figure .
Figure 8
Schematic of p-type semiconductor on exposure to reductant gas.
Schematic of p-type semiconductor on exposure to reductant gas.In contrast to n-type ones, as the temperature
increases, the resistance
variation of p-type semiconductors toward the reducing gases decreases.
Therefore, p-type semiconductors have relatively lower operating temperatures
than n-type ones.[7]In practical sensors,
the value of resistance needs to return back
to the initial value after evacuation of the analyte from the chamber.[7] As can be seen in Figure , in all concentrations, the resistance has
returned to the initial value after removing the formaldehyde from
the chamber. It is a good confirmation for the reusability (or reversibility)
of the sensor. Furthermore, for every concentration, sensor measurements
were repeated three times, and as it can be seen in Figure , similar results were obtained
which proves the repeatability of the fabricated sensor.A comparison
between the performances of the sensor for formaldehyde
and some other VOCs is shown in Figure and the real-time response of the sensor to ethanol,
methanol, water, acetone, and acetonitrile is shown in Figure S2. For this comparison, the response
of the sensor was calculated usingwhere R is considered as
the electrical resistance of the film on exposure to the analyte and R0 is the electrical resistance of film on exposure
to air.
Figure 9
Sensor response to 100 ppm of different analytes.
Sensor response to 100 ppm of different analytes.All tests were performed at 100 ppm concentration of analytes
at
room temperature with 18–20% RH. According to the data presented
in Figure , for different
analytes at the similar condition, the highest response was achieved
for the formaldehyde. Response of the sensor to 100 ppm of water vapor
was also measured, and no significant sensor response was observed.
It means that the proposed sensing material has shown good stability
against moisture. This observation can be related to the hydrophobic
nature of the ZIF-8 structure.[33]As mentioned before, ZIF-8 lacks conductivity, and its electrical
resistance is much more than can be measured by common multimeters.
So, pure ZIF-8cannot be used as a sensing material of the resistive
sensor and should be used with some conductive materials to be able
to exhibit electrical signals. So, a composite of ZIF-8 with MWCNTs
was used in this work. As we know, MWCNTs are used as gas-sensing
materials too, and their presence helps the sensing process. However,
since the surface area of ZIF-8 is much more than that of MWCNTs,
the sensitivity of the ZIF-8/MWCNTcomposite is obviously higher than
that of pure MWCNTs. Furthermore, in the absence of the analyte, the
MWCNT sensor was unable to reach the initial resistance (Figure ).
Figure 10
Response of ZIF-8/MWCNT
sensor and pure MWCNT sensor to different
concentrations of formaldehyde at room temperature.
Response of ZIF-8/MWCNT
sensor and pure MWCNT sensor to different
concentrations of formaldehyde at room temperature.Real-time resistive response of the sensor after exposure
to different
formaldehydeconcentrations is shown in Figure . After introducing formaldehyde into the
chamber, it took some time until the resistance reached a plateau.
This time interval is known as the response time, and it depends on
the concentration of the analyte. Response and recovery times of the
sensor give us an idea about how fast the sensor works. In sensor
reports, for evaluation of the response time, t90 is measured, which is defined as the time needed for the
sensor to reach from the initial equilibrium state to 90% of the final
equilibrium state after analyte entrance. Based on the achieved data, t90 for the analyte concentration of 5 and 100
ppm was 0.2 and 1.28 min, respectively, which shows the fast response
of the sensor. Also, the recovery time for the obtained sensor is
within seconds, which demonstrates the fast performance of the sensor.
Figure 11
Real-time
resistive response of the sensor in exposure to 5–100
ppm of formaldehyde.
Real-time
resistive response of the sensor in exposure to 5–100
ppm of formaldehyde.Since RH usually affects
the sensor performance, it is necessary
to consider its probable effect on sensor evaluations. Therefore,
the sensor performance was compared under different RHconditions.
For this purpose, first, a specified amount of water was injected
into the evacuated chamber to create a specific amount of RH, and
the system was allowed to reach the stable condition. Then, 50 ppm
formaldehyde was introduced into the chamber, and resistance variations
were recorded. Figure shows the resistance variations during time in the presence of 20,
40, and 60% RH. It is evident from this figure that at humid environments,
the response of the sensor has decreased a little and the presence
of water vapors in the environment has increased the response time.
Nevertheless, even under these conditions, high and fast response
could be observed. It is notable that after evacuation of the chamber,
for reaching RH of 20%, water vapor with a concentration of more than
6000 ppm was introduced into the chamber, which is much higher than
formaldehydeconcentration in this condition (50 ppm).
Figure 12
Effect of
RH on sensor response for detection of 50 ppm formaldehyde.
Effect of
RH on sensor response for detection of 50 ppm formaldehyde.Stability is an important parameter which tells
how long a sensor
can work without any remarkable changes in performance. For testing
the sensor stability, the fabricated sensor was tested for a couple
of months, and its response to formaldehyde vapors at three different
concentrations was compared. Figure shows that no significant change was seen in the sensor
performance during this period.
Figure 13
Response of the sensor on exposure to
25, 50, and 75 ppm formaldehyde
during the time.
Response of the sensor on exposure to
25, 50, and 75 ppm formaldehyde
during the time.For evaluation of sensor
performance, the calibration curve is
used, which depicts how the output signal of an analytical device
changes with the different concentrations of a specific analyte and
the derived calibration function is generally used for determining
the unknown concentrations of the analyte.[6]The calibration curve of formaldehyde is exhibited in Figure and shows an almost
linear relationship between the response of the sensor and the concentration
of formaldehyde vapor with a correlation coefficient (R2) of 0.9985.
Figure 14
Calibration curve of the sensor in the concentration
range of 5–100
ppm formaldehyde.
Calibration curve of the sensor in the concentration
range of 5–100
ppm formaldehyde.The minimum concentration
of vapor at which the gas sensor still
supplies reliable signals is defined as the limit of detection (LOD).
LOD is the lowest amount of an analyte that a sensor can distinguish
from the absence of the analyte at a known confident level. A lower
LOD shows higher sensitivity.[6] The signal
value of LOD (yLOD) is calculated by:where yb is the
mean value of blank signal (the intercept of calibration curve) and Sb is the standard deviation of the blank measurements
and is calculated by:[34]where y is the experimental signal of every concentration, y̅ is the theoretical
value calculated by the equation of calibration curve for every given
concentration, and n is the number of different concentrations
used to plot the calibration curve. Then, LOD in terms of concentration
is calculated from yLOD. According to
the achieved calibration function for formaldehyde and the above equations,
LOD for formaldehyde detection by the ZIF-8/MWCNT sensor was calculated
as low as 4.83 ppm. It proves that in this range of formaldehydeconcentration
(above 5 ppm), the sensor gives reliable responses.
Conclusions
Nanocomposite of ZIF-8 nanoparticles and functionalized-MWCNTs
was synthesized at room temperature and used as the sensing material
onto IDEs to fabricate a resistive gas sensor. The achieved ZIF-8/MWCNT
nanocomposite was used for detection of formaldehyde vapors at room
temperature (25–27 °C) and showed fast and high responses
because of the high surface area of the nanocomposite (1412.76 m2/g). LOD for formaldehyde was calculated as low as 4.83 ppm,
and the response of this sensor to formaldehyde was found higher than
some other vapors, including methanol, ethanol, acetone, acetonitrile,
and water with the same concentration. The effect of RH on the gas
response was studied as well and the sensor showed good performance
under different RHconditions. In addition, contrary to metal-oxide
sensors that are used under high temperatures, this sensor is used
at room temperature. To the best of our knowledge, this is the first
report on ZIF-8 as the main sensing material of resistive gas sensor
working at room temperature for the detection of formaldehyde.