CN114956010A - SnO 2 -MoSe 2 Preparation method of composite material, MEMS sulfur dioxide sensor and application thereof - Google Patents
SnO 2 -MoSe 2 Preparation method of composite material, MEMS sulfur dioxide sensor and application thereof Download PDFInfo
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Abstract
The invention relates to SnO 2 ‑MoSe 2 A preparation method of a composite material, an MEMS sulfur dioxide sensor and application thereof belong to the technical field of MEMS gas sensors. SnO described in the invention 2 ‑MoSe 2 The preparation method of the composite material comprises the following steps: (1) MoSe 2 The preparation of (1): sodium molybdate and selenium powder are taken as raw materials, sodium borohydride and absolute ethyl alcohol are sequentially added to carry out hydrothermal reaction, and MoSe is obtained through post-treatment 2 A nanomaterial; (2) SnO 2 ‑MoSe 2 Preparing a composite material: dissolving MoSe by ethanol 2 Then adding SnCl 4 •5H 2 O, placing the mixture in a high-pressure reaction kettle for reaction; cooling to room temperature, sequentially carrying out solid-liquid separation and drying, and finally obtaining the productAnnealing treatment is carried out under argon. The MEMS sulfur dioxide sensor prepared by the invention has the advantages of high sensitivity, quick response and recovery time and high selectivity.
Description
Technical Field
The invention relates to SnO 2 -MoSe 2 A preparation method of a composite material, an MEMS sulfur dioxide sensor and application thereof belong to the technical field of MEMS gas sensors.
Background
Sulfur dioxide (SO) 2 ) Is a colorless, highly toxic and highly irritant air pollutant, SO 2 Is oxidized into SO 3 Subsequent reaction with rain water will result in the formation of acid rain, which can irritate the skin and ulcers, reduce soil fertility, corrode buildings, and increase the acidity of the water. In addition, sulfur dioxide gas poses a serious threat to human health. Inhale low concentration SO 2 The gas can cause chemical burns and irritate the nose, throat and respiratory tract. Exposure of humans to SO by the American Occupational Safety and Health Administration (OSHA) 2 The threshold limit of (2) is set at 5 ppm and the long-term exposure limit is 2 ppm.
In recent years, many studies on sulfur dioxide detection have long response recovery time, or gas detection response values are not prominent enough on the premise of ensuring the response recovery time.
CN104089995A discloses a sulfur dioxide sensor based on anodic aluminum oxide nanowires and a preparation method thereof, wherein the anodic aluminum oxide nanowires are coated on electrodes of the sulfur dioxide sensor and subjected to surface modification by mixed solution of palladium chloride, anhydrous cobalt chloride and thiourea or titanium dioxide, and the preparation method comprises pretreatment, oxidation, surface modification and sensor preparation. The sensor of the invention has the advantages of low cost, quick response, short desorption time, good repeatability and high accuracy.
CN101986149A discloses an electrode material, a sensor and a preparation method thereof for measuring sulfur dioxide gas, which includes: a substrate and a sulfur dioxide oxidation catalyst deposited on the substrate, the sulfur dioxide oxidation catalyst comprising: 3-10wt% of a hydrophilic aerogel; 10-30wt% of a hydrophobic fluoropolymer adhesive; 60-87wt% gold. Also discloses a manufacturing method of the electrode material and a sensor containing the electrode material. The sensor formed by the electrode material for measuring the sulfur dioxide has good measurement stability under a low-humidity environment.
The products prepared by the above patents all adopt an electrochemical principle, and have oxidation-reduction reaction on electrodes, so that the service life is short, and the industrial application is not facilitated.
Disclosure of Invention
The invention aims to provide SnO 2 -MoSe 2 The preparation method of the composite material is simple and feasible, and the prepared composite material has larger specific surface area and catalytic cycle stability; the invention is based on SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor prepared from the composite material has high sensitivity, quick response and recovery time and high selectivity; the invention also provides application of the MEMS sulfur dioxide sensor, which effectively reduces the resistance value of the detection resistor and has high detection accuracy and precision.
SnO described in the invention 2 -MoSe 2 The preparation method of the composite material comprises the following steps:
（1）MoSe 2 the preparation of (1): sodium molybdate and selenium powder are taken as raw materials, sodium borohydride and absolute ethyl alcohol are sequentially added to carry out hydrothermal reaction, and MoSe is obtained through post-treatment 2 A nanomaterial;
（2）SnO 2 -MoSe 2 preparing a composite material: dissolving MoSe by ethanol 2 Then adding SnCl 4 •5H 2 O, placing the mixture in a high-pressure reaction kettle for reaction; cooling to room temperature, sequentially carrying out solid-liquid separation and drying, and finally annealing the obtained product under argon to obtain the SnO 2 -MoSe 2 A composite material.
In the step (1), preferably, the post-treatment comprises: when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifugally washing with water and ethanol, and drying; and putting the obtained solid in a sodium hydroxide solution, carrying out water bath, cooling to room temperature, continuing to centrifugally wash with water and ethanol, and finally drying.
In the step (2), preferably, the mixture is placed in a high-pressure reaction kettle at the temperature of 200-240 ℃ for reaction for 25-30 hours.
In the step (2), the obtained product is preferably annealed at a heating rate of 1 ℃/min for 2-3 hours under argon gas at 300-350 ℃.
In step (2), preferably, MoSe 2 With SnCl 4 •5H 2 The mass ratio of O is 1: 2-4.
Preferably, SnO 2 -MoSe 2 The preparation method of the composite material comprises the following steps:
① MoSe 2 the preparation method comprises the following steps:
a simple and mild hydrothermal method is adopted, and the specific operation is as follows:
weighing 2g of sodium molybdate and 2g of selenium powder by using a balance, placing the sodium molybdate and the selenium powder in a beaker, adding 20mL of distilled water, and stirring the mixture by using a magnetic stirrer to fully and uniformly mix the mixture;
then 0.4g of sodium borohydride is weighed and slowly dripped into the uniformly mixed solution, and the solution is continuously stirred in the dripping process to be uniformly mixed; then weighing 30mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into the solution, and stirring the solution for 40min by using a magnetic stirrer to fully and uniformly mix the solution;
then, pouring the solution into a reaction kettle for hydrothermal reaction; when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifuging and washing the liquid for a plurality of times by using water and ethanol, and then drying the liquid in a drying oven at 60 ℃;
placing the obtained solid in a sodium hydroxide solution, carrying out water bath for 3h at 85 ℃, and after cooling to room temperature, continuing to carry out centrifugal washing by using water and ethanol; then drying the mixture in a 60 ℃ oven to obtain the MoSe 2 And (3) nano materials.
②SnO 2 -MoSe 2 Preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.2g SnCl 4 •5H 2 Adding the mixture into the mixed solution, stirring for 30 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 200 ℃ for reaction for 30 hours;
cooling to room temperature, performing solid-liquid separation with centrifuge, drying in 100 deg.C vacuum drying oven for 24 hr, and cooling to 300 deg.C under argonAnnealing at a heating rate of 1 ℃/min for 2 hours to obtain SnO 2 -MoSe 2 A nanocomposite.
SnO mentioned 2 -MoSe 2 The MEMS sulfur dioxide sensor prepared from the composite material comprises the following preparation steps:
(1) cleaning the micro-heating plate and the tube shell, adhering the micro-heating plate and the tube shell by using a chip mounter, using a special adhesive, and then curing for 4 hours to achieve the adhesive strength between the micro-heating plate and the tube shell;
(2) after the micro-hotplate is bonded with the tube shell, carrying out micro-hotplate lead bonding by using a 25-micron gold wire by using a gold wire bonding machine;
(3) the bonded micro-heating plate and the tube shell are sprayed with nano-materials by using a micro-electronic printer, a nozzle with the diameter of 60 mu m is used for spraying the nano-materials on the micro-heating plate uniformly, and then the materials are cured, so that the bonding strength of the materials is increased;
(4) uniformly dispensing specific sealant around the tube shell by using an automatic dispenser, sealing the tube cap, and curing the device for 4 hours after sealing to achieve the bonding property between the tube shell and the tube cap;
(5) and packaging the micro-hotplate by using a universal 8 pin surface-mounted ceramic packaging base, wherein the length, width and height of a finished product are only 5mm 1.05mm, and the device can be directly attached to a printed circuit board after the packaging is finished.
The invention adopts a micro-hot plate suitable for deposition of sensitive materials, and the dimension of the shape is only 1mm by 0.3 mm. The micro-hotplate has good thermal response performance and heating efficiency, and is low in heating power consumption, fast in thermal response and small in heating hysteresis. Compared with the traditional ceramic tube type and planar type, the ceramic tube type and planar type has great advantages in heating power consumption (only 60mW at 400-500 ℃) and thermal response time (20-25 ms).
The MEMS sulfur dioxide sensor is attached to a printed circuit board and used for detecting the concentration of ammonia.
When the MEMS sulfur dioxide sensor is used for detecting ammonia gas, two voltages are applied: heater voltage (V) H ) And a test voltage (V) C ）。Wherein V H The sensor is provided with a specific working temperature, and a direct current power supply or an alternating current power supply can be used. Vout is the voltage across the load Resistance (RL) of the sensor series. V C The voltage for testing load resistance RL is supplied by DC power supply. The specific application is shown in figure 1.
SnO mentioned 2 -MoSe 2 When the MEMS sulfur dioxide sensor made of the composite material is used for detecting sulfur dioxide, the mechanism is as follows:
SnO 2 -MoSe 2 follows a surface charge model, which can be explained by the change in the composite resistance in different target gases. SnO 2 And MoSe 2 Is a typical n-type semiconductor material whose electrons are the majority carriers. In air, oxygen molecules are absorbed to the surface of the sensing material by trapping free electrons, forming oxygen anions (O) 2 - ). The reaction process is as follows:
with pure SnO 2 And MoSe 2 Material comparison, SnO 2 -MoSe 2 The composite material improves the SO pair 2 Sensing performance, which may be due to n-type SnO 2 And n-type MoSe 2 An n-n heterojunction is formed between the two. SnO 2 And MoSe 2 Has work functions of 4.9 and 4.6 eV, band widths of 3.6 and 1.3 eV, and electron affinities of 4.3 and 3.9 eV, respectively. Thus, since SnO 2 And MoSe 2 The difference in work function, both follow the electron affinity model and drive the electron flow. When two sensitive materials are in contact with each other, electrons will be in MoSe with high Fermi level 2 SnO transition to low fermi level 2 Until their fermi levels reach equilibrium. In the energy band of SnO 2 And MoSe 2 Is bent at the interface of (a), wherein the depletion layer is in MoSe 2 Is formed in SnO 2 Resulting in the formation of an n-n heterojunction at the interface of the two materials. When SnO 2 -MoSe 2 When the material is exposed to air, oxygen molecules are converted into O 2 - The barrier height increases, and this process increases the resistance of the sensor. When SnO 2 -MoSe 2 Composite material and reducing SO 2 When gas comes into contact, SO 2 The gas molecules may react with O 2 - Reacting and releasing electrons, thereby breaking the balance of fermi levels. SnO 2 Then to MoSe 2 Some electrons are injected until the Fermi level reaches a new balance, and the process causes the depletion layer and the accumulation layer of the electrons to be narrowed, the barrier height to be reduced, and the SnO is further reduced 2 -MoSe 2 Electrical resistance of the composite material.
SnO mentioned 2 -MoSe 2 A schematic diagram of the sensing mechanism and energy band of a MEMS sulfur dioxide sensor made of composite material is shown in figure 2.
Compared with the prior art, the invention has the following beneficial effects:
(1) SnO prepared by the invention 2 -MoSe 2 The composite material has larger specific surface area and catalytic cycle stability;
(2) the MEMS sulfur dioxide sensor prepared by the invention has high sensitivity, quick response and recovery time, and good consistency and reproducibility; the invention can keep the response recovery time at 18s and 47s under the concentration of 20ppm, and the response value is kept about 30.9 percent, thereby greatly improving the limitation of the existing gas-sensitive material;
(3) when the MEMS sulfur dioxide sensor is used for detecting sulfur dioxide, the detection accuracy and precision are high;
(4) when the MEMS sulfur dioxide sensor is used for detecting sulfur dioxide, the micro heating plate is arranged, so that the gas adsorption and desorption speeds are accelerated, the resistance value of the detection resistor can be effectively reduced, and the detection and the design of related hardware circuits are facilitated;
(5) the invention adopts the MEMS process, can effectively adjust the voltage at two ends of the heating resistor in real time according to the change of the environmental temperature, and further automatically adjust the heating power of the heating resistor, thereby better controlling the temperature of the gas sensitive layer to reach the working temperature.
Drawings
FIG. 1 is a circuit diagram of a test for detecting sulfur dioxide using a MEMS sulfur dioxide sensor;
FIG. 2 is a schematic diagram of the sensing mechanism and energy band of the MEMS sulfur dioxide sensor for detecting sulfur dioxide;
FIG. 3 is SnO 2 、MoSe 2 、SnO 2 -MoSe 2 XRD spectrum of (1);
FIG. 4 is the SnO 2 -MoSe 2 XPS spectra of the composite;
FIG. 5 is the SnO 2 -MoSe 2 Scanning electron micrographs of the composite;
FIG. 6 is based on said SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor of the composite material has a relationship graph of the change of the resistance value with time under different sulfur dioxide concentrations;
FIG. 7 is based on said SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor of the composite material is a graph of the response value of the MEMS sulfur dioxide sensor under different sulfur dioxide concentrations along with the change of time;
FIG. 8 is based on said SnO 2 -MoSe 2 A fitted plot of the response and sulfur dioxide concentration of a MEMS sulfur dioxide sensor of the composite material;
FIG. 9 is based on said SnO 2 -MoSe 2 A response-recovery curve graph of the MEMS sulfur dioxide sensor made of the composite material to 20ppm sulfur dioxide gas at 350 ℃;
FIG. 10 is based on said SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor of the composite material is used for testing repeated response of different sulfur dioxide concentrations;
FIG. 11 is based on said SnO 2 -MoSe 2 The usage temperature of the MEMS sulfur dioxide sensor made of the composite material is plotted as a function of voltage.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to these examples.
In the examples, the starting materials were all commercially available except where otherwise specified.
Example 1
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material comprises the following steps:
（1）MoSe 2 the preparation method comprises the following steps:
weighing 2g of sodium molybdate and 2g of selenium powder by using a balance, placing the sodium molybdate and the selenium powder in a beaker, adding 20mL of distilled water, and stirring by using a magnetic stirrer to fully and uniformly mix the sodium molybdate and the selenium powder;
then 0.4g of sodium borohydride is weighed and slowly dripped into the uniformly mixed solution, and the solution is continuously stirred in the dripping process to be uniformly mixed; then weighing 30mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into the solution, and stirring the solution for 40min by using a magnetic stirrer to fully and uniformly mix the solution;
then, pouring the solution into a reaction kettle for hydrothermal reaction; when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifuging and washing the liquid by using water and ethanol for a plurality of times, and then drying the liquid in a drying oven at 60 ℃;
placing the obtained solid in a sodium hydroxide solution, carrying out water bath for 3 hours at 85 ℃, and after cooling to room temperature, continuing to carry out centrifugal washing by using water and ethanol; then drying the mixture in a 60 ℃ oven to obtain MoSe 2 And (3) nano materials.
（2）SnO 2 -MoSe 2 Preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.2g SnCl 4 •5H 2 Adding the mixture into the mixed solution, stirring for 30 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 200 ℃ for reaction for 30 hours;
cooling to room temperature, performing solid-liquid separation with a centrifuge, drying in a vacuum drying oven at 100 deg.C for 24 hr, and annealing at 300 deg.C under argon at 1 deg.C/min for 3 hr to obtain SnO 2 -MoSe 2 A nanocomposite.
Based on the above SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor made of the composite material comprises the following preparation steps:
(1) cleaning a micro-heating plate with the size, length, width and height of 1mm, 0.3mm and a tube shell, adhering the micro-heating plate and the tube shell by using a chip mounter, using a special adhesive (brand: ABLESTIK, model: 144a chip adhesive), and then curing for 4 hours;
(2) after the micro-hotplate is bonded with the tube shell, carrying out micro-hotplate lead bonding by using a 25-micron gold wire by using a gold wire bonding machine;
(3) spraying nano materials on the micro-heating plate and the tube shell after bonding by using a micro-electronic printer, uniformly spraying the nano materials on the micro-heating plate by using a 60-micrometer nozzle, and then curing the materials;
(4) uniformly dispensing a specific sealant around the tube shell by using an automatic dispenser, sealing the tube cap, and curing the device for 4 hours after sealing to achieve the bonding property between the tube shell and the tube cap;
(5) and packaging the micro-hotplate by using a universal 8-pin surface-mounted ceramic packaging base, wherein the length, width and height of a finished product are only 5mm, 5mm and 1.05mm, and the packaged device can be directly attached to a printed circuit board.
Example 2
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material comprises the following steps:
（1）MoSe 2 the preparation method comprises the following steps:
weighing 2g of sodium molybdate and 4g of selenium powder by using a balance, placing the sodium molybdate and the selenium powder in a beaker, adding 20mL of distilled water, and stirring the mixture by using a magnetic stirrer to fully and uniformly mix the mixture;
then 0.5g of sodium borohydride is weighed and slowly dripped into the uniformly mixed solution, and the solution is continuously stirred in the dripping process to be uniformly mixed; then, 45mL of absolute ethyl alcohol is weighed and poured into the solution, and the solution is stirred for 55min by a magnetic stirrer to be fully and uniformly mixed;
then, pouring the solution into a reaction kettle for hydrothermal reaction; when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifuging and washing the liquid with water and ethanol for a plurality of times, and then drying the liquid in a drying oven at 55 ℃;
placing the obtained solid in a sodium hydroxide solution, carrying out water bath at 85 ℃ for 3.5h, cooling to room temperature, and then continuing to carry out centrifugal washing by using water and ethanol; then drying the mixture in a 65 ℃ oven to obtain the MoSe 2 And (3) nano materials.
（2）SnO 2 -MoSe 2 Preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.4g SnCl 4 •5H 2 Adding the O into the mixed solution, stirring for 35 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 240 ℃ for reaction for 25 hours;
cooling to room temperature, performing solid-liquid separation with a centrifuge, drying in a vacuum drying oven at 100 deg.C for 26 hr, and annealing at 350 deg.C under argon at 1 deg.C/min for 2 hr to obtain SnO 2 -MoSe 2 A nanocomposite.
Based on the above SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor of composite material was prepared by the same procedure as in example 1.
Example 3
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material comprises the following steps:
（1）MoSe 2 the preparation method comprises the following steps:
weighing 3g of sodium molybdate and 2g of selenium powder by using a balance, placing the sodium molybdate and the selenium powder in a beaker, adding 20mL of distilled water, and stirring the mixture by using a magnetic stirrer to fully and uniformly mix the mixture;
then 0.4g of sodium borohydride is weighed and slowly dripped into the uniformly mixed solution, and the solution is continuously stirred in the dripping process to be uniformly mixed; then weighing 30mL of absolute ethyl alcohol, pouring the absolute ethyl alcohol into the solution, and stirring the solution for 35min by using a magnetic stirrer to fully and uniformly mix the solution;
then, pouring the solution into a reaction kettle for hydrothermal reaction; when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifuging and washing the liquid by using water and ethanol for a plurality of times, and then drying the liquid in a drying oven at 55 ℃;
placing the obtained solid in a sodium hydroxide solution, carrying out water bath at 85 ℃ for 3.5h, cooling to room temperature, and then continuing to carry out centrifugal washing by using water and ethanol; then drying in an oven at 55 ℃ to obtain the MoSe 2 And (3) nano materials.
（2）SnO 2 -MoSe 2 Preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.3g SnCl 4 •5H 2 Adding the O into the mixed solution, stirring for 30 minutes, and placing the mixture into a 230 ℃ high-pressure reaction kettle for reaction for 27 hours;
cooling to room temperature, performing solid-liquid separation with a centrifuge, drying in a vacuum drying oven at 100 deg.C for 24 hr, and annealing at 335 deg.C under argon at 1 deg.C/min for 2.5 hr to obtain SnO 2 -MoSe 2 A nanocomposite.
Based on the above SnO 2 -MoSe 2 The MEMS sulfur dioxide sensor of composite material was prepared by the same procedure as in example 1.
SnO prepared as in example 1 2 -MoSe 2 The composite and MEMS sulfur dioxide sensor were subjected to the following tests:
for SnO 2 、MoSe 2 、SnO 2 -MoSe 2 XRD test was performed, and as shown in fig. 3, the crystalline phase of the prepared material was analyzed by XRD. SnO 2 The characteristic peak of (A) appears at 26.62 o 、34.05 o 、37.94 o 、51.92 o 、54.51 o 、62.15 o And 65.37 o Respectively with SnO 2 The (110), (101), (200), (211), (220), (310) and (112) crystal planes of (A) and (B) correspond to each other. MoSe 2 The characteristic peak of (2) appears at 13.53 o 、31.62 o 、37.68 o 、46.82 o And 55.96 o Where, respectively, correspond to MoSe 2 The (002), (100), (103), (105) and (110) crystal planes of (A), (B), (C), (100), (103), (105) and (110). SnO 2 /MoSe 2 The XRD pattern of the composite nano material contains all original SnO 2 And MoSe 2 Indicating successful synthesis of the composite.
From SnO 2 /MoSe 2 Peaks such as Mo 3d, Se 3d, Sn 3d and O1 s can be clearly observed in the XPS spectrum of the composite material, which shows the existence of four elements of Mo, Se, Sn and O, and particularly shown in figure 4.
As can be seen from the Scanning Electron Microscope (SEM) image in FIG. 5, the appearance structure of the composite material and flower-like MoSe 2 Similarly. However, since MoSe 2 Is coated with a plurality of SnO 2 Modified to become rough and also to show SnO 2 Successfully attached to MoSe 2 On the surface of (a).
The performance of the sensor was tested as follows:
as shown in fig. 6 and 7, the response S of the sensor is defined as:
wherein R is a Representing the resistance value, R, of the sensor in air g Is shown at SO 2 Resistance in the gas. By noting exposure to different SO 2 The change in resistance at gas concentrations (1-100 ppm) based on said SnO was investigated 2 -MoSe 2 Gas sensing properties of MEMS sulfur dioxide sensors of composite materials. It can be seen from the figure that with SO 2 The response values of all sensors are obviously increased when the concentration is increased. MEMS Sulfur dioxide sensor pairs 1, 5, 10, 20, 50, 100 and 100 ppm SO 2 The response values for the gas are about 7.3, 14.5, 21.8, 30.9, 38.2 and 47.3, respectively.
As shown in FIG. 8, based on said SnO 2 -MoSe 2 Fitted plot of response and sulfur dioxide concentration for MEMS sulfur dioxide sensor of composite material, where the X-axis is SO 2 The Y-axis is the response value of the sensor, and the fitting formula is as follows:
Y=8.8924ln（x）+3.8058；
coefficient of fit (R) thereof 2 ) Is 0.9659.
As shown in FIG. 9, based on said SnO 2 -MoSe 2 Response-recovery curves for the composite MEMS sulfur dioxide sensor at 350 c for 20ppm sulfur dioxide gas were 18s and 47s for MEMS sulfur dioxide sensor response/recovery time, respectively.
Repeatability is an important factor in the practical application of gas sensors. As shown in FIG. 10, the SnO based on the above was studied 2 -MoSe 2 The MEMS sulfur dioxide sensor of the composite material showed repeated response test patterns for different sulfur dioxide concentrations (5, 10 and 20 ppm). The resistance value of the sensor can be fully restored to the initial state in each cycle of the test, indicating good repeatability.
As shown in FIG. 11, is based on said SnO 2 -MoSe 2 The graph of the change relation between the use temperature and the voltage of the MEMS sulfur dioxide sensor made of the composite material can be seen from the attached drawings, the voltage at two ends of the heating resistor can be effectively adjusted in real time according to the change of the environmental temperature, and then the heating power of the heating resistor is automatically adjusted, so that the temperature of the gas sensitive layer is better controlled to reach the working temperature.
The application example is as follows:
the MEMS sulfur dioxide sensor prepared by the invention is applied to a workshop of a detection chemical plant, and particularly, the sensor is installed in a place where sulfur dioxide is easy to leak in an intelligent chemical industry park due to toxic and harmful gases generated by raw materials, production processes and the like, the installation height is 0.3-0.6m away from the ground, and clearance and access channels not less than 0.5m are reserved between the place where a probe is installed and peripheral pipelines and equipment.
Comparative example 1
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material is the same as that of the embodiment 1 except that:
SnO 2 -MoSe 2 preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding into 30mL ethanol solution, and magnetically treatingContinuously stirring for half an hour by using a force stirrer to uniformly mix;
weighing 0.3g SnCl 4 •5H 2 Adding the mixture into the mixed solution, stirring for 30 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 200 ℃ for reaction for 30 hours;
after the mixture is cooled to room temperature, a centrifuge is used for carrying out solid-liquid separation on the mixture, the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24 hours, and finally, the obtained product is annealed for 3 hours at the temperature rise rate of 1 ℃/min under argon at the temperature of 300 ℃, so that the volume mass ratio of the obtained product is 1: 5 SnO 2 -MoSe 2 A nanocomposite.
For the finally prepared SnO 2 -MoSe 2 The composite material is tested, and compared with the comparative example 1, the composite material in the example 1 has larger specific surface area, better stability, quicker response recovery time and higher sensitivity.
Comparative example 2
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material is the same as that of the embodiment 1 except that:
SnO 2 -MoSe 2 preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.5g of SnCl 4 •5H 2 Adding the mixture into the mixed solution, stirring for 30 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 200 ℃ for reaction for 30 hours;
after the mixture is cooled to room temperature, a centrifuge is used for carrying out solid-liquid separation on the mixture, the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24 hours, and finally, the obtained product is annealed for 2 hours at the temperature rise rate of 1 ℃/min under argon at the temperature of 300 ℃, so that the volume mass ratio of the obtained product is 1: SnO 6 2 -MoSe 2 A nanocomposite.
For the finally prepared SnO 2 -MoSe 2 The composite material is tested, and compared with the comparative example 2, the composite material in the example 1 has larger specific surface area, better stability, faster response recovery time and higher sensitivity.
Comparative example 3
SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material is the same as that of the embodiment 1 except that:
SnO 2 -MoSe 2 preparing a composite material:
0.1g of MoSe was weighed using a balance 2 Adding the mixture into 30mL of ethanol solution, and continuously stirring for half an hour by using a magnetic stirrer to uniformly mix the mixture;
weighing 0.7g SnCl 4 •5H 2 Adding the mixture into the mixed solution, stirring for 30 minutes, and placing the mixture into a high-pressure reaction kettle at the temperature of 200 ℃ for reaction for 30 hours;
after the mixture is cooled to room temperature, a centrifuge is used for carrying out solid-liquid separation on the mixture, the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24 hours, and finally, the obtained product is annealed for 2 hours at the temperature rise rate of 1 ℃/min under argon at the temperature of 300 ℃, so that the volume mass ratio of the obtained product is 1: SnO of 7 2 -MoSe 2 A nanocomposite.
For the finally prepared SnO 2 -MoSe 2 The composite material is tested, and compared with the comparative example 3, the composite material in the example 1 has larger specific surface area, better stability, faster response recovery time and higher sensitivity.
TABLE 1 Performance of Sensors prepared based on the composites of examples 1-3 and comparative examples 1-3
| Distinguishing | Response time(s) | Recovery time(s) | Response value (%) |
| Example 1 | 18 | 47 | 30.9 |
| Example 2 | 22 | 50 | 28.4 |
| Example 3 | 23 | 52 | 28.1 |
| Comparative example 1 | 27 | 58 | 26.5 |
| Comparative example 2 | 30 | 60 | 25.4 |
| Comparative example 3 | 34 | 63 | 25.1 |
Remarking: the concentration of sulfur dioxide was 20ppm during the measurement.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still make modifications to the technical solutions described in the foregoing embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. SnO (stannic oxide) 2 -MoSe 2 The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
（1）MoSe 2 the preparation of (1): sodium molybdate and selenium powder are taken as raw materials, sodium borohydride and absolute ethyl alcohol are sequentially added to carry out hydrothermal reaction, and MoSe is obtained through post-treatment 2 A nanomaterial;
（2）SnO 2 -MoSe 2 preparing a composite material: dissolving MoSe by ethanol 2 Then adding SnCl 4 •5H 2 O, placing the mixture in a high-pressure reaction kettle for reaction; cooling to room temperature, sequentially carrying out solid-liquid separation and drying, and finally annealing the obtained product under argon to obtain the SnO 2 -MoSe 2 A composite material.
2. A SnO according to claim 1 2 -MoSe 2 The preparation method of the composite material is characterized by comprising the following steps: in the step (1), the post-treatment comprises: when the temperature of the oven is reduced to below room temperature, pouring out the liquid in the reaction kettle, alternately centrifugally washing with water and ethanol, and drying; and putting the obtained solid in a sodium hydroxide solution, carrying out water bath, cooling to room temperature, continuing to centrifugally wash with water and ethanol, and finally drying.
3. A SnO according to claim 1 2 -MoSe 2 The preparation method of the composite material is characterized by comprising the following steps: in the step (2), the mixture is placed in a high-pressure reaction kettle at the temperature of 200 ℃ and 240 ℃ for reaction for 25 to 30 hours.
4. A SnO according to claim 1 2 -MoSe 2 The preparation method of the composite material is characterized by comprising the following steps: in the step (2), the obtained product is annealed for 2-3 hours at the heating rate of 1 ℃/min under argon gas at the temperature of 300-350 ℃.
5. A SnO according to claim 1 2 -MoSe 2 The preparation method of the composite material is characterized by comprising the following steps: in step (2), MoSe 2 With SnCl 4 •5H 2 The mass ratio of O is 1: 2-4.
6. The SnO based on claim 1 2 -MoSe 2 MEMS sulfur dioxide sensor of combined material preparation, its characterized in that: the preparation method comprises the following preparation steps:
(1) cleaning the micro-heating plate and the tube shell, adhering the micro-heating plate and the tube shell by using a chip mounter, and then curing;
(2) performing micro-hotplate lead bonding by using a gold wire;
(3) spraying nano materials on the micro-heating plate and the tube shell after the bonding is finished by using a micro-electronic printer, spraying the nano materials on the micro-heating plate, and then curing the materials;
(4) uniformly dispensing the sealant around the tube shell, sealing the tube cap, and curing;
(5) and packaging the micro-hotplate by using the surface-mounted ceramic packaging base to obtain the MEMS sulfur dioxide sensor.
7. The MEMS sulfur dioxide sensor of claim 6, wherein: the heating power consumption of the micro-hotplate needs 60mW at 400-500 ℃, and the thermal response time is 20-25 ms.
8. The MEMS sulfur dioxide sensor of claim 6, wherein: in the step (2), a 25 μm gold wire was used.
9. The MEMS sulfur dioxide sensor of claim 6, wherein: the size, width and height of the prepared MEMS ammonia gas sensor finished product are 5mm, 5mm and 1.05 mm.
10. The application of the MEMS sulfur dioxide sensor is characterized in that: the MEMS sulfur dioxide sensor of any of claims 6-9 attached to a printed circuit board for detecting sulfur dioxide concentration.
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