CN108318544A - Based on In2O3The NO of-ZnO compound nano sensitive materials2Gas sensor and preparation method thereof - Google Patents
Based on In2O3The NO of-ZnO compound nano sensitive materials2Gas sensor and preparation method thereof Download PDFInfo
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- CN108318544A CN108318544A CN201810238515.3A CN201810238515A CN108318544A CN 108318544 A CN108318544 A CN 108318544A CN 201810238515 A CN201810238515 A CN 201810238515A CN 108318544 A CN108318544 A CN 108318544A
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
One kind is based on three-dimensional counter opal structure In2O3The enhanced room temperature NO of visible light of ZnO compound nano sensitive materials2Gas sensor and preparation method thereof belongs to conductor oxidate gas sensor technical field.For heater-type device architecture, the Al of two parallel, cyclic annular and separate gold electrodes is carried by outer surface2O3Ceramic tube substrate, coated in the three-dimensional counter opal structure In on ceramic tube outer surface and gold electrode2O3ZnO compounds nano sensitive material and the white light-emitting diodes composition being arranged perpendicular to ceramic tube axial direction.Test result shows the sensor to 5ppm NO2High sensitivity up to 54.3, Monitoring lower-cut can reach 250ppb, have quick response and regeneration rate, have good selectivity and repeatability.Therefore it is known that sensor of the present invention is in atmospheric environment NO2Room temperature detects and visible light sensitizing type field of electronic devices has broad application prospects.
Description
Technical field
The invention belongs to conductor oxidate gas sensor technical fields, and in particular to one kind is based on three-dimensional counter opal
Structure I n2O3The enhanced room temperature NO of visible light of-ZnO compound nano sensitive materials2Gas sensor and preparation method thereof.
Background technology
In recent years, with the aggravation of air environmental pollution, safety accident take place frequently and fossil energy, military project, aviation navigate
The rapid development in the fields such as it.Gas sensor is to receive the attention of height as the one big of sensory field.Wherein, make
For the semiconductor-type gas sensor of one important branch of gas sensor, due to it is low with price, all solid state, small,
The advantages that integrability and progressed into the visual field of people.Although in the research of conductor oxidate gas sensor
Through obtaining prodigious progress, but in order to meet it in the requirement of each detection field, still need to further increase sensor
Sensitivity, selectivity and stability, and reduce gas sensor operating temperature.
The optimum working temperature of traditional conductor oxidate gas sensor is generally within the scope of 150~400 DEG C, herein
Under the conditions of just can guarantee device obtain excellent sensitivity and quickly response recovery characteristics.This, which allows for traditional devices all, needs to pacify
The heaters such as heater strip, heating plate are filled, this not only makes sensor structure become complicated, also can be caused by higher operating temperature
The negative effects such as non-intrinsically safe, bad stability.
In recent years, in terms of sensitive material research, one-dimensional, two-dimentional, three-dimensional structure nano material, special appearance are partly led
Oxide body and complex chemical compound are widely used in the gas-sensitive property for improving gas sensor as sensitive material.Wherein, three
Counter opal structure is tieed up due to widely being paid close attention to special three-dimensional macropore oldered array structure, compared to a wiener
Rice noodles, nanometer rods, the other structures such as two-dimensional nano-film, with larger specific surface area, thus can provide more work
Property site is conducive to semi-conducting material and is come into full contact with gas molecule and the diffusion of gas molecule.In addition, due to its long-range
Ordered big hole structure, thus in visible-range have periodically variable refractive index, to slow photon effect with it is more
Rescattering, this is conducive to improve absorption and utilization of the semi-conducting material to light.Based on this special porous structure, to prepare tool
There is the nanocomposite of three-dimensional counter opal structure, the sensitivity characteristic of conductor oxidate sensor can be further increased,
Because the compound and assembling of different conductor oxidate sensitive materials can form local N-N contacts or P-N contacts improve
The carrier mobility of sensing material.Recently, in addition to the exploitation of new gas sensitive and the improvement of preparation process, people is studied both at home and abroad
Member by way of light (ultraviolet light, visible light) excitation it has also been found that can significantly improve the quick of conductor oxidate gas sensor
Feel characteristic and reduces the operating temperature of sensor.
In short, the research of light sensitizing type gas sensor is at the early-stage, it is in high sensitivity, low-power consumption, low operating temperature
The excellent properties that aspect is shown receive much attention.Carry out designing and preparing for the composite material with special construction, and is answered
For the gas sensor of visible light sensitizing type, strive so that the reduction of gas sensor operating temperature, right convenient for integrated and application
There is highly important scientific meaning in the application of enlargement gas sensor.
Invention content
It is an object of the present invention to provide one kind based on three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials
The enhanced room temperature NO of visible light2Gas sensor, and a kind of preparation three-dimensional counter opal structure efficiently, easy is provided simultaneously
In2O3The method of-ZnO compound nano sensitive materials, and a kind of new device architecture is proposed to realize room temperature under visible light stimulus
NO2Gas detection.
The present invention is first using kayexalate, sodium bicarbonate and styrene as raw material, and water is as solvent, persulfuric acid
Potassium prepares polystyrene microsphere powder as initiator, using surfactant- free emulsion polymerization；Then, by polyphenyl second made from previous step
Alkene microsphere powder is dispersed in progress sulfonation processing in concentrated sulfuric acid solution so that Surfaces of Polystyrene Microparticles contains thiocyanate (SO3 -H+) functional group, to complete the preparation of template；Again using the polystyrene microsphere after sulfonation as template, with nitric hydrate indium and hydration
Zinc nitrate is raw material, and the mixed solution of water, dilute hydrochloric acid and aqueous hydrogen peroxide solution utilizes ultrasonic spray pyrolysis as solvent
It is successfully prepared three-dimensional counter opal structure In2O3- ZnO compound precursors, then calcining obtains three-dimensional anti-albumen in air
Stone structure In2O3- ZnO compound nano sensitive materials.
It is of the present invention a kind of based on three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials it is visible
The enhanced room temperature NO of light2Gas sensor, device are heater-type structure, parallel, cyclic annular and divide each other with two by outer surface
The Al of vertical gold electrode2O3Ceramic tube substrate, coated in the three-dimensional counter opal structure on ceramic tube outer surface and gold electrode
In2O3- ZnO compounds nano sensitive material and the white light-emitting diodes (LED ,~480nm) being arranged perpendicular to ceramic tube axial direction
Composition, wherein white light-emitting diodes distance Al2O3The vertical range of ceramic tube is 1~1.5cm.Sensor at work, two pole of white light
Pipe passes to direct current to provide visible light source for sensor, direct current when by measuring in different atmosphere between two gold electrodes
It hinders resistance value and realizes measurement NO2The function of concentration, test result show the sensor to 5ppm NO2High sensitivity up to 54.3, inspection
It surveys lower limit and can reach 250ppb, there is quick response and regeneration rate, have good selectivity and repeatable.It therefore can be with
It learns, sensor of the present invention is in atmospheric environment NO2Room temperature detection and visible light sensitizing type field of electronic devices have wide
Application prospect.In the present invention, three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials are prepared by following steps
It arrives：
(1) first by the kayexalate of 0.15~0.50g, the sodium bicarbonate of 0.05~0.35g, 10~50mL
Styrene is added sequentially in 150~500mL deionized waters, under nitrogen atmosphere (10~50sccm of nitrogen flow rate) heating water bath
(50~80 DEG C of water bath heating temperature) simultaneously stirs；After stirring 0.5~1.5h, the potassium peroxydisulfate of 0.05~0.35g is added, continues
(10~50sccm of nitrogen flow rate) heating water bath (50~80 DEG C of water bath heating temperature) and 15~20h of stirring under nitrogen atmosphere；
(2) after reaction, obtained product water and ethyl alcohol are alternately subjected to centrifuge washing, by obtained product into
Row drying obtains polystyrene microsphere powder；
(3) by the polystyrene microsphere powder that 5~15g steps (2) obtain be added to 10~50mL, mass fraction 95~
In 98% concentrated sulfuric acid solution, after heating water bath (30~60 DEG C of water bath heating temperature) stirs 4~6h, obtained product is spent
Ionized water and ethyl alcohol alternately cleaning 5~7 times, are then dried at 70~90 DEG C, obtaining sulfonated polystyrene microballoon, (microballoon is straight
Diameter：~100nm)；
(4) In of the sulfonated polystyrene microsphere powder for the 0.05~0.18g for again obtaining step (3), 0.05~0.25g
(NO3)3·4.5H2O, the Zn (NO of 0.05~0.25g3)2·6H2O be added sequentially to containing 0.10~0.20mL, concentration 0.1~
0.2M dilute hydrochloric acid and 0.10~0.20mL, 25~30% aqueous hydrogen peroxide solution of mass fraction 8~20mL deionized waters in, stir
40~80min is mixed until it is all dissolved；
(5) solution for obtaining step (4) ullrasonic spraying at 500~800 DEG C thermally decomposes 2~4h, in ullrasonic spraying heat
Always with nitrogen as carrier gas (400~700sccm of nitrogen flow rate) during decomposition reaction, and in ullrasonic spraying thermal decomposer
Tail portion conical flask in collect powder；By alternately cleaning 5~7 times of obtained product deionized water and ethyl alcohol, then 70
It is dried at~90 DEG C, then carries out 2~5h of calcining at 400~600 DEG C, to obtain three-dimensional counter opal knot of the present invention
Structure In2O3- ZnO compound nano sensitive materials；
Heretofore described sensor uses heater-type structure, preparation process as follows：
(1) three-dimensional counter opal structure In is taken2O3- ZnO compound nano sensitive materials, with isopropanol in mass ratio 0.25
~0.5:1 ratio is uniformly mixed and forms slurry；With hairbrush dip slurry coating on the surface carry two it is parallel, cyclic annular and that
The Al of this discrete gold electrode2O3Ceramic tube outer surface, makes it that gold electrode be completely covered；The thickness of compound nano sensitive material is
15~30 μm；Al2O3The internal diameter of ceramic tube is 0.6~0.8mm, and outer diameter is 1.0~1.5mm, and length is 4~5mm；Single gold electricity
The width of pole is 0.4~0.5mm, and the spacing of two gold electrodes is 0.5~0.6mm；The platinum filament wire drawn on gold electrode, length
Degree is 4~6mm；
(2) by coated Al2O3Ceramic tube is sintered 2~5h at 200~350 DEG C, then will be ceramic by platinum filament wire
Pipe is welded on general heater-type hexagonal tube socket；
(3) white light-emitting diodes finally is placed above heater-type hexagonal tube socket, makes white light-emitting diodes perpendicular to Al2O3Ceramics
Pipe, to obtain based on three-dimensional counter opal structure In2O3The enhanced room temperature of visible light of-ZnO compound nano sensitive materials
NO2Gas sensor.
Operation principle：
It when light photon energy is consistent with semiconductor energy gap, is irradiated on conductor oxidate, valence can be caused
Having electronic, which is excited, crosses forbidden band arrival conduction band formation photo-generate electron-hole pair, to reduce material resistance.Simultaneously, it is seen that light
Excitation process influences the chemical reaction equilibrium state between material surface and adsorbed gas.In air, semiconductor material surface is logical
It crosses physical absorption and chemisorption forms absorption oxygen O2 -.When radiation of visible light, semiconductor, which is excited, generates light induced electron
Hole pair, the electronics on conduction band has strong reducing property, and the hole in valence band has strong oxidizing property.The electrons and holes one of generation
Part is compound in vivo, and with adsorption gas redox reaction occurs for another part diffusive migration to surface.O2 -Ion loses
De-electromation is oxidized to O by photohole2.According under Persistent Excitation effect, under test gas is more easy to participate in light induced electron sky visible light
The redox reaction in cave, so that material electric conductivity significant changes.Visible light is according to the energy for improving semiconductor surface absorption
Power and adsorption site concentration so that chemisorption efficiency improves, to make gas sensor just have at room temperature under test gas
Preferable sensitive performance.We define the sensitivity S of sensor herein：S=Rgas/Rair, wherein RairIn air for sensor
Resistance, RgasFor sensor contacts NO2Resistance afterwards.
Advantage of the present invention：
(1) present invention is prepared for three using the polystyrene microsphere after sulfonation as template with ultrasonic spray pyrolysis method
Tie up counter opal structure In2O3- ZnO compound nano sensitive materials, to develop the enhanced room temperature NO of high-performance visible light2Gas
Sensor provides a kind of effective sensitive material.
(2) gas sensor prepared by the present invention realizes at room temperature under visible light continuous action to NO2Height
Imitate fast slowdown monitoring.
(3) In that the present invention uses2O3- ZnO compound nano sensitive materials have three-dimensional anti-protein structure, this special
Structure more active site can be provided, be conducive to semi-conducting material and come into full contact with gas molecule, be conducive to gas point
Son diffusion, can realize quick adsorption and desorption.In addition, due to its long-range order macroporous structure, thus in visible-range
With periodically variable refractive index, to have slow photon effect and multiple scattering, this is conducive to improve semi-conducting material pair
The absorption and utilization of light.
(4) sensor stability of exploitation is good, operating temperature is low, highly reliable.
(5) innovative introducing white light-emitting diodes substitutes traditional thermal excitation source ni-Cd as visible light excitation source and adds
Heat coil advantageously reduces operating temperature, reduces power consumption, improves device service life and application range, is that visible light is enhanced
The integrated and application of temperature sensor provides theoretical foundation.
(6) In that the present invention makes2O3Zno-based NO2Gas sensor manufacture craft is simple, and preparation method step is easy,
It is of low cost, it is suitble to industrial batch production.
Description of the drawings
Fig. 1 is of the present invention based on three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials it is visible
The enhanced room temperature NO of light2The structural schematic diagram of gas sensor；
Fig. 2 is of the present invention based on three-dimensional counter opal structure In2O3The SEM of-ZnO compound nano sensitive materials
Figure, wherein the amplification factor of (a) figure is 50000 times, (b) amplification factor of figure is 10000 times；
Fig. 3 is of the present invention based on three-dimensional counter opal structure In2O3The TEM of-ZnO compound nano sensitive materials
Scheme (a), HRTEM schemes (b) and SAED figures (c).
Fig. 4 be in the embodiment of the present invention sensor when operating temperature is room temperature under visible light illumination to gas with various
Selective schematic diagram；
Fig. 5 is sensor operating temperature under visible light illumination in the embodiment of the present invention and comparative example 1 and comparative example 2
For room temperature when, in 0.25~5ppm NO2Atmosphere medium sensitivity and gas concentration function curve.
Fig. 6 is that sensor works temperature under visible light illumination in the embodiment of the present invention 1 and comparative example 1 and comparative example 2
Device sensitivity-NO when degree is room temperature2Concentration profiles.
Fig. 7 is long-time stability of sensor when operating temperature is room temperature under visible light illumination in the embodiment of the present invention
Curve.
As shown in Figure 1, the names of the parts are：Al2O3Ceramic tube 1, platinum line 2, annular gold electrode 3, white light-emitting diodes 4,
In2O3- ZnO compounds nano sensitive material 5；
As shown in Fig. 2, (a) it can be seen from the figure that In2O3- ZnO compound nano sensitive materials are three-dimensional counter opal microballoon
Structure, while we can also be observed that microballoon is made of some nano particles.(b) the three-dimensional anti-albumen of it can be seen from the figure that
Stone In2O3ZnO microsphere, good dispersion, size ratio is more uniform, a diameter of 0.8~1.5 μm of each microballoon；
As shown in figure 3, Fig. 3 (a) is the In of synthesis2O3The TEM of-ZnO schemes, and sphere shows apparent light and shade pair in figure
Than further demonstrating its three-dimensional counter opal structure.Again to three-dimensional counter opal In2O3HRTEM has been carried out in ZnO microsphere
It tests (Fig. 3 (b)), the distance that can be calculated on a direction between adjacent crystal planes is 0.206nm, is on another direction
0.253nm corresponds to In2O3(422) and (400) crystal face；It is 0.19nm there is also the distance between adjacent crystal planes on a direction,
Corresponding to ZnO (102) crystal face.Fig. 3 (c) is corresponding selective electron diffraction photo, can be obtained from selective electron diffraction photo
Know, the three-dimensional counter opal In of these compositions2O3The nano particle of ZnO microsphere is typical polycrystal.
As shown in figure 4, under visible light illumination operating temperature be room temperature when embodiment in sensor to NO2With higher
Sensitivity.
As shown in figure 5, when operating temperature is room temperature under visible light illumination, embodiment 1 and comparative example 1 and comparative example 2
Middle NO2NO of the sensitivity of sensor in various concentration2Change curve under (0.25~5ppm) atmosphere.As can be seen from the figure
With detection gas NO2Concentration increase, the sensitivity of sensor is with NO2The raising of concentration, sensitivity increase.It is worth noting
Be the sensor NO that can be detected in embodiment compared with comparative example 1 and comparative example 22Concentration limit is 0.25ppm, corresponding
Sensitivity is 4.4, and the Monitoring lower-cut of sensor is relatively low in embodiment 1.And it compared with comparative example 1 and comparative example 2, is passed in embodiment
The sensitivity of sensor has obtained significant raising.
As shown in fig. 6, when operating temperature is room temperature to device under visible light illumination, the sensitivity of all devices with
NO2The increase of concentration and increase, and all have certain linear relationship.Wherein, sensor sheet reveals best gas in embodiment
Quick characteristic.But it can be seen that sensor has lower Monitoring lower-cut only in embodiment.
It is illustrated in figure 7 the long-time stability of sensor in embodiment.In 30 days time, sensor is tested can
When operating temperature is room temperature under light-exposed irradiation, to 5ppm NO2Sensitivity.In 30 days time, the fluctuation range of sensitivity
It is 55~65, has substantially remained in a stable range.It can be seen that sensor shows good stability.
Specific implementation mode
Comparative example 1：
With three-dimensional counter opal In2O3Microballoon makes the enhanced room temperature NO of visible light as nano sensitive material2Gas sensing
Device, specific manufacturing process are as follows：
(1) styrene of the kayexalate of 0.3g, the sodium bicarbonate of 0.25g, 30mL are added sequentially to first
In 300mL deionized waters, (nitrogen flow rate under nitrogen atmosphere：30sccm) heating water bath (water bath heating temperature：70 DEG C) stirring.
After stirring 1h, the potassium peroxydisulfate of 0.15g is added, continues (nitrogen flow rate under nitrogen atmosphere：30sccm) (water-bath adds heating water bath
Hot temperature：70 DEG C) stirring 18h；
(2) after reaction, obtained product water and ethyl alcohol are alternately subjected to centrifuge washing, by obtained product into
Row drying obtains polystyrene microsphere powder；
(3) the polystyrene microsphere powder that 10g steps (2) obtain is added to the concentrated sulfuric acid (mass fraction 98%) of 40mL
In solution.Heating water bath (water bath heating temperature：40 DEG C) stirring 5h after, by obtained product deionized water and ethyl alcohol replace it is clear
It washes 6 times, is then dried at 80 DEG C, obtain sulfonated polystyrene microballoon；
(4) In (NO of the sulfonated polystyrene microsphere powder for the 0.15g for again obtaining step (3), 0.24g3)3·
4.5H2O is added sequentially to that (mass fraction is containing 0.16mL dilute hydrochloric acid (a concentration of 0.1M), 0.3mL aqueous hydrogen peroxide solutions
30%) in 15mL deionized waters, stirring 50min is until it is all dissolved；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 3.5h, anti-in ullrasonic spraying thermal decomposition
It should be in the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the cone of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in shape bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.It is dry
After, product is subjected to calcining 3h at 500 DEG C；
(6) appropriate three-dimensional counter opal structure In is taken2O3Microsphere nano sensitive material, with isopropanol 0.5mg in mass ratio:
1mg is uniformly mixed to form slurry.Slurry coating, which is dipped, with hairbrush carries two gold electricity parallel, cyclic annular and separate on the surface
The Al of pole2O3Ceramic tube outer surface, makes it that gold electrode be completely covered.The nano sensitive material thickness of ceramic tube outer surface is 20 μm
(Al2O3The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.8mm, and the width of 2 annular gold electrodes is 0.8mm, two
A electrode spacing is 1.8mm, and two platinum filaments are connected on each gold electrode and make pin, the length of platinum filament is 9mm)；
(7) coated ceramic tube at 300 DEG C is sintered 3h, is then welded on ceramic tube by platinum filament wire general
On heater-type hexagonal tube socket；
(8) white light-emitting diodes finally is placed above heater-type hexagonal tube socket, makes white light-emitting diodes perpendicular to Al2O3Ceramics
Pipe, to obtain based on three-dimensional counter opal structure In2O3The enhanced room temperature NO of-ZnO compound nano sensitive material visible lights2
Gas sensor.
Comparative example 2：
The enhanced room temperature NO of visible light is made using three-dimensional counter opal ZnO microsphere as sensitive material2Gas sensor,
Specific manufacturing process is as follows：
(1) styrene of the kayexalate of 0.3g, the sodium bicarbonate of 0.25g, 30mL are added sequentially to first
In 300mL deionized waters, (nitrogen flow rate under nitrogen atmosphere：30sccm) heating water bath (water bath heating temperature：70 DEG C) stirring.
After stirring 1h, the potassium peroxydisulfate of 0.15g is added, continues (nitrogen flow rate under nitrogen atmosphere：30sccm) (water-bath adds heating water bath
Hot temperature：70 DEG C) stirring 18h；
(2) after reaction, obtained product water and ethyl alcohol are alternately subjected to centrifuge washing, by obtained product into
Row drying obtains polystyrene microsphere powder；
(3) the polystyrene microsphere powder that 10g steps (2) obtain is added to the concentrated sulfuric acid (mass fraction 98%) of 40mL
In solution.Heating water bath (water bath heating temperature：40 DEG C) stirring 5h after, by obtained product deionized water and ethyl alcohol replace it is clear
It washes 6 times, is then dried at 80 DEG C, obtain sulfonated polystyrene microballoon；
(4) Zn (NO of the sulfonated polystyrene microsphere powder for the 0.15g for again obtaining step (3), 0.24g3)2·6H2O
It is added sequentially to containing 0.16mL dilute hydrochloric acid (a concentration of 0.1M), 0.3mL aqueous hydrogen peroxide solutions (mass fraction 30%)
In 15mL deionized waters, stirring 50min is until it is all dissolved；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 3.5h, anti-in ullrasonic spraying thermal decomposition
It should be in the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the cone of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in shape bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.It is dry
After, product is subjected to calcining 3h at 500 DEG C；
(6) appropriate three-dimensional counter opal structure ZnO microsphere nano sensitive material is taken, with isopropanol 0.5mg in mass ratio:
1mg is uniformly mixed to form slurry.Slurry coating, which is dipped, with hairbrush carries two gold electricity parallel, cyclic annular and separate on the surface
The Al of pole2O3Ceramic tube outer surface, makes it that gold electrode be completely covered.The nano sensitive material thickness of ceramic tube outer surface is 20 μm
(Al2O3The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.8mm, and the width of 2 annular gold electrodes is 0.8mm, two
A electrode spacing is 1.8mm, and two platinum filaments are connected on each gold electrode and make pin, the length of platinum filament is 9mm)；
(7) coated ceramic tube at 300 DEG C is sintered 3h, is then welded on ceramic tube by platinum filament wire general
On heater-type hexagonal tube socket；
(8) white light-emitting diodes finally is placed above heater-type hexagonal tube socket, makes white light-emitting diodes perpendicular to Al2O3Ceramics
Pipe, to obtain three-dimensional counter opal structure In2O3The enhanced room temperature NO of-ZnO compound nano sensitive material visible lights2Gas
Sensor.
Embodiment 1：
With three-dimensional counter opal In2O3ZnO microsphere makes the enhanced room temperature NO of visible light as sensitive material2Gas sensing
Device, specific manufacturing process are as follows：
(1) styrene of the kayexalate of 0.3g, the sodium bicarbonate of 0.25g, 30mL are added sequentially to first
In 300mL deionized waters, (nitrogen flow rate under nitrogen atmosphere：30sccm) heating water bath (water bath heating temperature：70 DEG C) stirring.
After stirring 1h, the potassium peroxydisulfate of 0.15g is added, continues (nitrogen flow rate under nitrogen atmosphere：30sccm) (water-bath adds heating water bath
Hot temperature：70 DEG C) stirring 18h；
(2) after reaction, obtained product water and ethyl alcohol are alternately subjected to centrifuge washing, by obtained product into
Row drying obtains polystyrene microsphere powder；
(3) the polystyrene microsphere powder that 10g steps (2) obtain is added to the concentrated sulfuric acid (mass fraction 98%) of 40mL
In solution.Heating water bath (water bath heating temperature：40 DEG C) stirring 5h after, by obtained product deionized water and ethyl alcohol replace it is clear
It washes 6 times, is then dried at 80 DEG C, obtain sulfonated polystyrene microballoon；
(4) In (NO of the sulfonated polystyrene microsphere powder for the 0.15g for again obtaining step (3), 0.12g3)3·
4.5H2O, the Zn (NO of 0.12g3)2·6H2O is added sequentially to containing 0.16mL dilute hydrochloric acid (a concentration of 0.1M), 0.3mL peroxidating
In the 15mL deionized waters of aqueous solution of hydrogen (mass fraction 30%), stirring 50min is until it is all dissolved；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 3.5h, anti-in ullrasonic spraying thermal decomposition
It should be in the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the cone of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in shape bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.It is dry
After, product is subjected to calcining 3h at 500 DEG C；
(6) appropriate three-dimensional counter opal structure In is taken2O3ZnO microsphere nano sensitive material, in mass ratio with isopropanol
0.5mg:1mg is uniformly mixed to form slurry.With hairbrush dip slurry coating carry on the surface two it is parallel, cyclic annular and divide each other
The Al of vertical gold electrode2O3Ceramic tube outer surface, makes it that gold electrode be completely covered.The nano sensitive material thickness of ceramic tube outer surface
For 20 μm of (Al2O3The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.8mm, and the width of 2 annular gold electrodes is
0.8mm, two electrode spacings are 1.8mm, and two platinum filaments are connected on each gold electrode and make pin, the length of platinum filament is 9mm)；
(7) coated ceramic tube at 300 DEG C is sintered 3h, is then welded on ceramic tube by platinum filament wire general
On heater-type hexagonal tube socket；
(8) white light-emitting diodes finally is placed above heater-type hexagonal tube socket, makes white light-emitting diodes perpendicular to Al2O3Ceramics
Pipe, to obtain three-dimensional counter opal structure In2O3The enhanced room temperature NO of-ZnO compound nano sensitive material visible lights2Gas
Sensor.
Claims (3)
1. one kind is based on three-dimensional counter opal structure In2O3The enhanced room temperature NO of visible light of-ZnO compound nano sensitive materials2
Gas sensor is heater-type structure, the Al of two parallel, cyclic annular and separate gold electrodes is carried by outer surface2O3Ceramics
Tube lining bottom, coated on ceramic tube outer surface and gold electrode nano sensitive material and perpendicular to ceramic tube axial direction setting
White light-emitting diodes forms；It is characterized in that：Nano sensitive material is three-dimensional counter opal structure In2O3- ZnO compound nanometers are quick
Feel material, and it is prepared by following steps,
(1) first by the benzene second of the kayexalate of 0.15~0.50g, the sodium bicarbonate of 0.05~0.35g, 10~50mL
Alkene is added sequentially in 150~500mL deionized waters, heating water bath and is stirred under nitrogen atmosphere；After stirring 0.5~1.5h,
The potassium peroxydisulfate of 0.05~0.35g is added, continue heating water bath under nitrogen atmosphere and stirs 15~20h；
(2) after reaction, obtained product water and ethyl alcohol are alternately subjected to centrifuge washing, obtained product is done
It is dry, obtain polystyrene microsphere powder；
(3) polystyrene microsphere powder that 5~15g steps (2) obtain is added to 10~50mL, mass fraction 95~98%
In concentrated sulfuric acid solution, after heating water bath stirs 4~6h, obtained product deionized water and ethyl alcohol are alternately cleaned 5~7 times,
Then it is dried at 70~90 DEG C, obtains sulfonated polystyrene microballoon；
(4) In of the sulfonated polystyrene microsphere powder for the 0.05~0.18g for again obtaining step (3), 0.05~0.25g
(NO3)3·4.5H2O, the Zn (NO of 0.05~0.25g3)2·6H2O be added sequentially to containing 0.10~0.20mL, concentration 0.1~
0.2M dilute hydrochloric acid and 0.10~0.20mL, 25~30% aqueous hydrogen peroxide solution of mass fraction 8~20mL deionized waters in, stir
40~80min is mixed until it is all dissolved；
(5) solution for obtaining step (4) ullrasonic spraying at 500~800 DEG C thermally decomposes 2~4h, is thermally decomposed in ullrasonic spraying
Always with nitrogen as carrier gas in reaction process, and powder is collected in the conical flask of the tail portion of ullrasonic spraying thermal decomposer；
Then it dries, then alternately cleaning 5~7 times of obtained product deionized water and ethyl alcohol 400~600 at 70~90 DEG C
2~5h of calcining is carried out at DEG C, to obtain three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials.
2. as described in claim 1 a kind of based on three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials can
Light-exposed enhanced room temperature NO2Gas sensor, it is characterised in that：White light-emitting diodes distance Al2O3The vertical range of ceramic tube is 1
~1.5cm.
3. described in claim 1 a kind of based on three-dimensional counter opal structure In2O3- ZnO compound nano sensitive materials it is visible
The enhanced room temperature NO of light2The preparation method of gas sensor, its step are as follows：
(1) three-dimensional counter opal structure In is taken2O3- ZnO compound nano sensitive materials, with isopropanol in mass ratio 0.25~
0.5:1 ratio is uniformly mixed and forms slurry；With hairbrush dip slurry coating carry on the surface two it is parallel, cyclic annular and each other
The Al of discrete gold electrode2O3Ceramic tube outer surface, makes it that gold electrode be completely covered；The thickness of compound nano sensitive material is 15
~30 μm；
(2) by coated Al2O3Ceramic tube is sintered 2~5h at 200~350 DEG C, is then welded ceramic tube by platinum filament wire
It is connected on general heater-type hexagonal tube socket；
(3) white light-emitting diodes finally is placed above heater-type hexagonal tube socket, makes white light-emitting diodes perpendicular to Al2O3Ceramic tube, from
And it obtains based on three-dimensional counter opal structure In2O3The enhanced room temperature NO of visible light of-ZnO compound nano sensitive materials2Gas
Sensor.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108732214A (en) * | 2018-08-29 | 2018-11-02 | 吉林大学 | Based on PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material |
| CN109342521A (en) * | 2018-10-15 | 2019-02-15 | 吉林大学 | The In of alkaline earth metal doping2O3Formaldehyde sensitive material and its application in formaldehyde examination |
| CN110736770A (en) * | 2019-10-16 | 2020-01-31 | 郑州大学 | N-GQDs modified 3DOM In2O3Composite material and preparation method and application thereof |
| CN110823965A (en) * | 2019-11-15 | 2020-02-21 | 东北师范大学 | Room temperature detection NO2Gas sensitive material and preparation method thereof |
| CN112557446A (en) * | 2020-10-27 | 2021-03-26 | 盐城工学院 | Moisture-resistant nano Zn-In2O3Three-dimensional structure sensor material and preparation method and application thereof |
| CN113155905A (en) * | 2021-03-03 | 2021-07-23 | 应急管理部天津消防研究所 | Ag modified ZnO-In2O3Preparation method of gas-sensitive material |
| CN114993972A (en) * | 2022-05-27 | 2022-09-02 | 江南大学 | ZnO nanowire and NO 2 Gas sensor, its preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458827A (en) * | 2014-12-15 | 2015-03-25 | 吉林大学 | NO2 gas sensor based on hollow spherical WO3 and preparation method of NO2 gas sensor based on the hollow spherical WO3 |
-
2018
- 2018-03-22 CN CN201810238515.3A patent/CN108318544A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458827A (en) * | 2014-12-15 | 2015-03-25 | 吉林大学 | NO2 gas sensor based on hollow spherical WO3 and preparation method of NO2 gas sensor based on the hollow spherical WO3 |
Non-Patent Citations (2)
| Title |
|---|
| JI-WOOK YOON ET AL.: "Trimodally porous SnO 2 nanospheres with three dimensional interconnectivity and size tunability: a one-pot synthetic route and potential application as an extremely sensitive ethanol detector", 《NPG ASIA MATERIALS》 * |
| TIANSHUANG WANG ET AL.: "Rational design of 3D inverse opal heterogeneous composite microspheres as excellent visible-light-induced NO2 sensors at room temperature", 《NANOSCALE》 * |
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| CN108732214A (en) * | 2018-08-29 | 2018-11-02 | 吉林大学 | Based on PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material |
| CN109342521A (en) * | 2018-10-15 | 2019-02-15 | 吉林大学 | The In of alkaline earth metal doping2O3Formaldehyde sensitive material and its application in formaldehyde examination |
| CN110736770A (en) * | 2019-10-16 | 2020-01-31 | 郑州大学 | N-GQDs modified 3DOM In2O3Composite material and preparation method and application thereof |
| CN110736770B (en) * | 2019-10-16 | 2022-04-19 | 郑州大学 | N-GQDs modified 3DOM In2O3Composite material and preparation method and application thereof |
| CN110823965A (en) * | 2019-11-15 | 2020-02-21 | 东北师范大学 | Room temperature detection NO2Gas sensitive material and preparation method thereof |
| CN112557446A (en) * | 2020-10-27 | 2021-03-26 | 盐城工学院 | Moisture-resistant nano Zn-In2O3Three-dimensional structure sensor material and preparation method and application thereof |
| CN113155905A (en) * | 2021-03-03 | 2021-07-23 | 应急管理部天津消防研究所 | Ag modified ZnO-In2O3Preparation method of gas-sensitive material |
| CN114993972A (en) * | 2022-05-27 | 2022-09-02 | 江南大学 | ZnO nanowire and NO 2 Gas sensor, its preparation and application |
| CN114993972B (en) * | 2022-05-27 | 2023-08-11 | 江南大学 | ZnO nanowire and NO 2 Gas sensor, its preparation and application |
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