CN108732214A - Based on PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material - Google Patents
Based on PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material Download PDFInfo
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- CN108732214A CN108732214A CN201810994969.3A CN201810994969A CN108732214A CN 108732214 A CN108732214 A CN 108732214A CN 201810994969 A CN201810994969 A CN 201810994969A CN 108732214 A CN108732214 A CN 108732214A
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- G—PHYSICS
- 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 being based on three-dimensional counter opal structure PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material, belongs to gas sensor technical field.The sensor of exploitation is heater-type structure, and 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 PdO In on ceramic tube outer surface and gold electrode2O3Compound nano sensitive material and the ni-Cd heating coil composition being placed in ceramic tube.The present invention develops a kind of high performance gas sensor to acetone with quick response, test result show the sensor to the high sensitivity of 100ppm acetone up to 52.3, Monitoring lower-cut can reach 0.5ppm, with quick response and regeneration rate, have good selectivity and repeatable.Sensor of the present invention has broad application prospects in acetone detection field of electronic devices.
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 PdO@In2O3The acetone gas sensor and preparation method thereof of compound nano sensitive material.
Background technology
In recent years, with the improvement of living standards and the development of medical technology, people are more next for early stage medical diagnosis on disease
More pay attention to.Wherein, the breath analysis using gas sensor as detection unit is as a kind of disease early diagnosis means, due to it
With Noninvasive, material benefit, it is quickly and easy the advantages that, occupy main status in personal health care monitoring field.It is reported that
The volatile organic compounds (VOCs) contained in characteristics of contaminated respiratory droplets gas, such as acetone (CH3COCH3) it can be used as biomarker use
In the diagnosis of diabetes.For example, observing that high acetone concentration is more than 1.8/1000000ths in the expiratory air of diabetic
(ppm), the artificial 0.3-0.9ppm of health.As the semiconductor-type gas sensor of one important branch of gas sensor, by
In its have many advantages, such as price is low, all solid state, small, integrability and progressed into the visual field of people.In order to pass through
Breast rail Accurate Diagnosis specified disease, the trace concentration that scentometer must breathe target biomarker are sensitive.It is low
In ppm or even lower than part per billion (ppb), and in the expiratory air of very moist (being usually 90% relative humidity, RH)
In to these biomarkers have selectivity.Still need to further increase sensitivity, selectivity and the stability of sensor.
In terms of sensitive material research, one-dimensional, two-dimentional, three-dimensional structure nano material, the semiconductor oxide of special appearance
Object and complex chemical compound are widely used in the gas-sensitive property for improving gas sensor as sensitive material.Wherein, three-dimensional anti-egg
White stone structure due to widely being paid close attention to special three-dimensional macropore oldered array structure, compared to one-dimensional nano line,
Nanometer rods, the other structures such as two-dimensional nano-film, with larger specific surface area, thus can provide more active sites
Point is conducive to semi-conducting material and is come into full contact with gas molecule and the diffusion of gas molecule.
It carries out noble metal by the method for dipping based on this special porous structure and supports, have three-dimensional anti-to prepare
The nanocomposite of opal structural can further increase the sensitivity characteristic of conductor oxidate sensor, first, your gold
Metal nano-particle has special catalysis characteristics；Secondly, noble metal nano particles are compound with conductor oxidate sensitive material
With can form local heterojunction, this will improve the carrier mobility of sensing material.
Therefore, carry out the conductor oxidate sensitive material with special construction design and prepare and noble metal
It supports and modifies, and be applied to the high performance acetone gas sensor of exploitation in expiration detection field with highly important
Meaning.
Invention content
It is an object of the present invention to provide one kind being based on three-dimensional counter opal structure PdO@In2O3Compound nano sensitive material
Acetone gas sensor and preparation method thereof.
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 polystyrene microsphere obtained
Powder is dispersed in progress sulfonation processing in concentrated sulfuric acid solution so that Surfaces of Polystyrene Microparticles contains thiocyanate (SO3 -H+) function
Group, to complete the preparation of template；It is water, dilute using nitric hydrate indium as raw material again using the polystyrene microsphere after sulfonation as template
The mixed solution of hydrochloric acid and aqueous hydrogen peroxide solution is successfully prepared three-dimensional anti-egg as solvent, using ultrasonic spray pyrolysis
White stone structure In2O3Presoma, then calcining obtains three-dimensional counter opal structure In in air2O3Nano material.It will obtain again
Three-dimensional counter opal structure In2O3Nano material is added in the ethanol solution containing palladium nitrate and stirs, and is stirred to solution change
It is dry.Finally, obtained powder is calcined in air, to obtain three-dimensional counter opal structure PdO@In2O3Compound nanometer is quick
Feel material.
It is of the present invention a kind of based on three-dimensional counter opal structure PdO@In2O3The acetone of compound nano sensitive material
Gas sensor, device are heater-type structure, and the Al of two parallel, cyclic annular and separate gold electrodes is carried by outer surface2O3
Ceramic tube substrate, coated in the three-dimensional counter opal structure PdO In on ceramic tube outer surface and gold electrode2O3Compound nanometer is quick
Sense material and the ni-Cd heating coil composition being placed in ceramic tube.At work, ni-Cd heating coil passes to direct current to sensor
The operating temperature of sensor is provided, passes through the D.C. resistance resistance value for measuring in different atmosphere between two gold electrodes and realizes and measure third
The function of ketone concentration, test result show the sensor to the high sensitivity of 100ppm acetone up to 52.3, Monitoring lower-cut can reach
0.5ppm has quick response and regeneration rate, has good selectivity and repeatable.Therefore it is known that the present invention
The sensor has broad application prospects in acetone detection field of electronic devices.In the present invention, three-dimensional counter opal structure
PdO@In2O3Compound nano sensitive material is prepared by following steps：
(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 40~80 DEG C of heating water baths and stir 0.5~
1.5h, then be added 0.05~0.35g potassium peroxydisulfate, continue under nitrogen atmosphere 40~80 DEG C of heating water baths and stir 15~
20h；
(2) after reaction, product water and the ethyl alcohol alternately centrifuge washing that will be obtained carry out obtained product
It is dry, obtain 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 40~80 DEG C of heating water baths stir 4~6h, obtained product deionized water and ethyl alcohol are handed over
For cleaning 5~7 times, is then dried at 70~90 DEG C, obtain sulfonated polystyrene microsphere powder；
(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 be added to containing 0.10~0.20mL dilute hydrochloric acid and 0.10~0.20mL aqueous hydrogen peroxide solutions 8~
In 20mL deionized waters, 40~80min of stirring is until it is all dissolved；A concentration of 0.1~0.2M of dilute hydrochloric acid, aquae hydrogenii dioxidi
The mass fraction of hydrogen peroxide is 25~30% in solution；
(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 during decomposition reaction, and powder is collected in the conical flask of the tail portion of ullrasonic spraying thermal decomposer
End；By alternately cleaning 5~7 times of obtained product deionized water and ethyl alcohol, then dried at 70~90 DEG C, then 400~
2~5h is calcined at 600 DEG C, to obtain three-dimensional counter opal structure In2O3Material, In2O3Material product quality is 50~
90mg；
(6) the three-dimensional counter opal structure In for obtaining 25~50mg steps (5)2O3Material is added to 3~6mL, palladium nitrate
Palladium nitrate (Pd (the NO of a concentration of 5.2~21at.%3)2·2H2O it) is stirred in ethanol solution, is stirred to solution exsiccation；Finally,
Obtained powder is calcined into 0.5~1.5h at 300~400 DEG C, to obtain three-dimensional counter opal structure PdO@In2O3It is compound
Object nano sensitive material, PdO@In2O3Material product quality is 20~45mg.
One kind being based on three-dimensional counter opal structure PdO@In2O3The acetone gas sensor of compound nano sensitive material
Preparation method, its step are as follows：
(1) PdO@In are taken2O3Compound nano sensitive material and isopropanol in mass ratio 0.25~0.5:1 ratio mixing
It is formed uniformly slurry；Slurry coating, which is dipped, with hairbrush carries two gold electrodes parallel, cyclic annular and separate on the surface
Al2O3Ceramic tube outer surface, makes it that gold electrode be completely covered；The thickness of compound nano sensitive material is 15~30 μm of (Al2O3
The internal diameter of ceramic tube is 0.6~0.8mm, and outer diameter is 1.0~1.5mm, and length is 4~5mm；The width of single gold electrode is 0.4
The spacing of~0.5mm, two gold electrodes are 0.5~0.6mm；The platinum filament wire drawn on gold electrode, the length of 4~6mm)；
(2) by coated Al2O3Ceramic tube is sintered 2~5h at 200~350 DEG C；
(3) coated ceramic tube is sintered to 2~5h at 200~350 DEG C, is then the nickel of 30~40 Ω by resistance value
Cadmium heating coil (the number of turns is 50~60 circles) passes through Al2O3Ceramic tube inside passes to direct current to provide operating temperature, work temperature
Degree is 85~110 DEG C.Ceramic tube is welded on general heater-type hexagonal tube socket finally by platinum filament wire；
(4) finally by sensor in 200~400 DEG C of air environments aging 5~7 days, to obtain three-dimensional counter opal
Structure PdO@In2O3Oxide semiconductor acetone gas sensor.
Operation principle：
As PdO@In2O3When benzylacetone gas sensor is placed in air, the oxygen molecule in air can be adsorbed on sensitive material
Electronics is simultaneously captured in the surface of material from its conduction band, forms Surface Oxygen ionic adsorption oxygen molecule with O2 -、O-Or O2-Mode deposit
, this can cause sensitive material electron concentration reduction, resistance increase.When sensor is placed in acetone gas under certain suitable temperature
When in body atmosphere, acetone gas molecule can be reacted with the oxonium ion for being adsorbed on sensitive material surface so that the electricity being captured
Son is released back into the energy band of sensitive material again so that electron concentration increases, and shows as PdO@In2O3The reduction of resistance value.At this
In we define the sensitivity S of sensor：S=Rair/Rgas, wherein RairFor the resistance between sensor in air two gold electrodes,
RgasFor the resistance between two gold electrodes after sensor contacts acetone.
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 In2O3Nano sensitive material, and three-dimensional counter opal structure PdO@are finally made by precious metal impregnation method
In2O3Compound nano sensitive material provides a kind of effective sensitive material for exploitation high-performance acetone gas sensor；
(2) the PdO@In that the present invention uses2O3Compound nano sensitive material has 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.The sensor of exploitation is low to acetone high sensitivity, Monitoring lower-cut, and stability is good
With it is highly reliable；
(3) the innovative introducing noble metal nano particles (PdO) of the present invention are used as catalyst, the introducing of PdO nano particles
The gas-sensitive property of sensor will be significantly improved；
(4) the PdO@In that the present invention makes2O3Benzylacetone gas 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 PdO@In2O3The acetone of compound nano sensitive material
The structural schematic diagram of gas sensor；
Fig. 2 is of the present invention based on three-dimensional counter opal structure PdO@In2O3The SEM of compound nano sensitive material
Figure, wherein the amplification factor of (a) figure is 50000 times, (b) amplification factor of figure is 100000 times；
Fig. 3 is of the present invention based on three-dimensional counter opal structure PdO@In2O3The TEM of compound nano sensitive material
Scheme (a), HRTEM schemes (b)；
Fig. 4 is sensor in the comparative example 1 of the present invention, embodiment 1, embodiment 2 and embodiment 3 at a temperature of different operating
Response to 100ppm acetone；
Fig. 5：Under 250 DEG C of operating temperature, sensed in comparative example 1 of the invention, embodiment 1, embodiment 2 and embodiment 3
Response of the device to a variety of different volatile organic compounds of 100ppm；
Fig. 6：Under 250 DEG C of operating temperature, sensed in comparative example 1 of the invention, embodiment 1, embodiment 2 and embodiment 3
Device is in 0.5~100ppm acetone medium sensitivity change curves；
Fig. 7：Under 250 DEG C of operating temperature, sensed in comparative example 1 of the invention, embodiment 1, embodiment 2 and embodiment 3
Functional relation between device sensitivity and gas concentration.
Fig. 8：Under 250 DEG C of operating temperature, the linearity curve steady in a long-term of sensor in the embodiment of the present invention 2.
As shown in Figure 1, the names of the parts are：Al2O3Ceramics pipe outer (1), platinum line (2), annular gold electrode (3), ni-Cd are closed
Gold thread circle (4), PdO@In2O3Compound nano sensitive material (5)；
As shown in Fig. 2, (a) it can be seen from the figure that PdO@In2O3Compound nano sensitive material is three-dimensional counter opal microballoon
The diameter of structure, microballoon is about 1.2 μm, while we can also be observed that microballoon is made of some nano particles.(b) figure
In it can be seen that three-dimensional counter opal PdO@In2O3There are PdO nano particles, nano particle good dispersion, size ratios for microsphere surface
It is more uniform；
As shown in figure 3, Fig. 3 (a) is the PdO@In of synthesis2O3Scheme, sphere shows apparent comparison of light and shade into one in figure
Step demonstrates its three-dimensional counter opal structure.Again to three-dimensional counter opal PdO@In2O3HRTEM tests (figure has been carried out in microballoon
3 (b)), the distance that can be calculated on a direction between adjacent crystal planes is 0.292nm, corresponds to In2O3(222) crystal face；Also deposit
The distance between adjacent crystal planes is 0.264nm in one direction, corresponds to PdO (101) crystal face, further, it is also possible to find that PdO receives
The average-size of rice grain is about 10nm；
As shown in figure 4, it may be seen that the sensitivity of sensor first rises with temperature declines again, very strong temperature is showed
Spend dependence.For unmodified In2O3For based sensor (sensor in comparative example 1), sensitivity is in 275 DEG C of conditions
Under reach peak value, it can be seen that sensitivity maxima only has 13.2.In contrast, by nano-particle modified three kinds of PdO
In2O3Material, three kinds of PdO@In2O3Based sensor (sensor in embodiment 1, embodiment 2 and embodiment 3) its sensitivity has
Different degrees of raising, and their optimum working temperature is also declined slightly.Under the conditions of 250 DEG C, embodiment 1, embodiment 2
Obtain maximum response (being respectively 25.84,50.93 and 30.45) simultaneously with sensor in embodiment 3.It is passed with comparative example 1
Sensor is compared, and it is sensor in embodiment 2 to behave oneself best, its sensitivity is sensor in comparative example 1 more than 3 times；
As shown in figure 5, under 250 DEG C of operating temperature, compared to sensor in comparative example 1, embodiment 1 and embodiment 3,
Sensor in embodiment 2 has preferable selectivity to acetone, and sensitivity is higher；
As shown in fig. 6, under 250 DEG C of operating temperature, sensed in comparative example 1, embodiment 1, embodiment 2 and embodiment 3
Change curve of the sensitivity of device under acetone (0.5~100ppm) atmosphere of various concentration.As can be seen from the figure with inspection
The concentration for surveying gas acetone increases, and the sensitivity of sensor is with the raising of acetone concentration, sensitivity increase.It is worth noting that
Compared with sensor in comparative example 1, embodiment 1 and embodiment 3, sensor acetone concentration lower limit that can be detected in embodiment 2
For 0.5ppm, corresponding sensitivity is 1.4, and the Monitoring lower-cut of sensor is relatively low in embodiment 2, and with comparative example 1, embodiment 1 and
Sensor is compared in embodiment 3, in embodiment 2 sensitivity of sensor obtained significant raising；
As shown in fig. 7, under 250 DEG C of operating temperature, the sensitivity of all devices with the increase of acetone concentration and
Increase, and all there is certain linear relationship.Wherein, sensor sheet reveals best gas-sensitive property in embodiment 2, and with compared with
Low Monitoring lower-cut；
It is illustrated in figure 8 the long-time stability of sensor in embodiment 2.In 30 days time, test in embodiment 2
Sensor is under 250 DEG C of operating temperature, the sensitivity to 100ppm acetone.In 30 days time, the fluctuation model of sensitivity
It is 44~53 to enclose, and has been 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 acetone gas sensor as nano sensitive material, specific to make
Process is as follows：
(1) styrene of the kayexalate of 0.4g, the sodium bicarbonate of 0.35g, 40mL are added sequentially to first
In 400mL deionized waters, 70 DEG C of heating water baths and 1.2h is stirred under nitrogen atmosphere, the potassium peroxydisulfate of 0.3g is then added, after
Continuous 70 DEG C of heating water baths under nitrogen atmosphere simultaneously stir 20h；
(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 of 40mL, mass fraction 98%
In solution, after 40 DEG C of heating water bath stirring 5h, by alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then 80
It is dried at DEG C, obtains sulfonated polystyrene microsphere powder；
(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 in the 15mL deionized waters containing 0.161mL dilute hydrochloric acid and 0.15mL aqueous hydrogen peroxide solutions, stirs 60min
Until it is all dissolved；A concentration of 0.15M of dilute hydrochloric acid, the mass fraction of hydrogen peroxide is 30% in aqueous hydrogen peroxide solution；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 4h, in ullrasonic spraying pyrolysis
In the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the taper of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.Dry knot
Product is carried out calcining 3h by Shu Hou at 500 DEG C, to obtain three-dimensional counter opal structure In2O3Material, In2O3Material product
Quality is 80mg；
(6) three-dimensional counter opal structure In made from certain mass is taken2O3(sensitive material quality is nano sensitive material
0.025mg) with isopropanol 0.4mg in mass ratio:1mg is uniformly mixed to form slurry.Appropriate slurry, which is dipped, with hairbrush is coated in city
Ceramic tube outer surface is sold, making it that the gold electrode of outer surface be completely covered, (internal diameter of tubular ceramic substrate is 0.7mm, and outer diameter is
1.1mm, length 4.5mm；Two cyclic annular gold electrodes being mutually parallel are come on its outer surface, the single width of two electrodes is
0.4mm, spacing 0.5mm；The platinum filament wire length drawn on gold electrode is 5mm)；
(7) coated ceramic tube at 300 DEG C is sintered 3h, ni-Cd heating coil is then passed through into Al2O3In ceramic tube
Portion passes to direct current to provide operating temperature.Ceramic tube is welded on general heater-type hexagonal tube socket finally by platinum filament wire
On, to obtain In2O3Base oxide semiconductor acetone sensor；
(8) finally by sensor in 300 DEG C of air environments aging 6 days, for use；
(9) sensitivity of the sensor to 100ppm acetone is tested at 250 DEG C.
Embodiment 1：
With three-dimensional counter opal PdO@In2O3Compound nano sensitive material makes acetone gas sensor, specific to make
It is as follows to make process：
(1) styrene of the kayexalate of 0.4g, the sodium bicarbonate of 0.35g, 40mL are added sequentially to first
In 400mL deionized waters, 70 DEG C of heating water baths and 1.2h is stirred under nitrogen atmosphere, the potassium peroxydisulfate of 0.3g is then added, after
Continuous 70 DEG C of heating water baths under nitrogen atmosphere simultaneously stir 20h；
(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 of 40mL, mass fraction 98%
In solution, after 40 DEG C of heating water bath stirring 5h, by alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then 80
It is dried at DEG C, obtains sulfonated polystyrene microsphere powder；
(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 in the 15mL deionized waters containing 0.161mL dilute hydrochloric acid and 0.15mL aqueous hydrogen peroxide solutions, stirs 60min
Until it is all dissolved；A concentration of 0.15M of dilute hydrochloric acid, the mass fraction of hydrogen peroxide is 30% in aqueous hydrogen peroxide solution；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 4h, in ullrasonic spraying pyrolysis
In the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the taper of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.Dry knot
Product is carried out calcining 3h by Shu Hou at 500 DEG C, to obtain three-dimensional counter opal structure In2O3Material, In2O3Material product
Quality is 80mg；
(6) the three-dimensional counter opal structure In for obtaining 30mg steps (5)2O3It is a concentration of that material is added to 5mL, palladium nitrate
Palladium nitrate (Pd (the NO of 5.2at.%3)2·2H2O it) is stirred in ethanol solution, is stirred to solution exsiccation；Finally, the powder that will be obtained
1h is calcined in end at 350 DEG C, to obtain three-dimensional counter opal structure PdO@In2O3Compound nano sensitive material PdO@In2O3
Material product quality is 25mg；
(7) PdO@In made from certain mass are taken2O3Compound nano sensitive material (sensitive material quality is 0.025mg)
With isopropanol 0.4mg in mass ratio:1mg is uniformly mixed to form slurry.Appropriate slurry, which is dipped, with hairbrush is coated in commercially available ceramic tube
Outer surface, making it that the gold electrode of outer surface be completely covered, (internal diameter of tubular ceramic substrate is 0.7mm, outer diameter 1.1mm, length
For 4.5mm；Two cyclic annular gold electrodes being mutually parallel are come on its outer surface, the single width of two electrodes is 0.4mm, and spacing is
0.5mm；The platinum filament wire length drawn on gold electrode is 5mm)；
(8) coated ceramic tube at 300 DEG C is sintered 3h, ni-Cd heating coil is then passed through into Al2O3In ceramic tube
Portion passes to direct current to provide operating temperature.Ceramic tube is welded on general heater-type hexagonal tube socket finally by platinum filament wire
On, to obtain PdO@In2O3Base oxide semiconductor acetone sensor；
(9) finally by sensor in 300 DEG C of air environments aging 6 days, for use；
(10) sensitivity of the sensor to 100ppm acetone is tested at 250 DEG C.
Embodiment 2：
With three-dimensional counter opal PdO@In2O3Compound nano sensitive material makes acetone gas sensor, specific to make
It is as follows to make process：
(1) styrene of the kayexalate of 0.4g, the sodium bicarbonate of 0.35g, 40mL are added sequentially to first
In 400mL deionized waters, 70 DEG C of heating water baths and 1.2h is stirred under nitrogen atmosphere, the potassium peroxydisulfate of 0.3g is then added, after
Continuous 70 DEG C of heating water baths under nitrogen atmosphere simultaneously stir 20h；
(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 of 40mL, mass fraction 98%
In solution, after 40 DEG C of heating water bath stirring 5h, by alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then 80
It is dried at DEG C, obtains sulfonated polystyrene microsphere powder；
(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 in the 15mL deionized waters containing 0.161mL dilute hydrochloric acid and 0.15mL aqueous hydrogen peroxide solutions, stirs 60min
Until it is all dissolved；A concentration of 0.15M of dilute hydrochloric acid, the mass fraction of hydrogen peroxide is 30% in aqueous hydrogen peroxide solution；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 4h, in ullrasonic spraying pyrolysis
In the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the taper of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.Dry knot
Product is carried out calcining 3h by Shu Hou at 500 DEG C, to obtain three-dimensional counter opal structure In2O3Material, In2O3Material product
Quality is 80mg；
(6) the three-dimensional counter opal structure In for obtaining 30mg steps (5)2O3It is a concentration of that material is added to 5mL, palladium nitrate
Palladium nitrate (Pd (the NO of 10.4at.%3)2·2H2O it) is stirred in ethanol solution, is stirred to solution exsiccation；Finally, the powder that will be obtained
1h is calcined in end at 350 DEG C, to obtain three-dimensional counter opal structure PdO@In2O3Compound nano sensitive material PdO@In2O3
Material product quality is 25mg；
(7) PdO@In made from certain mass are taken2O3Compound nano sensitive material (sensitive material quality is 0.025mg)
With isopropanol 0.4mg in mass ratio:1mg is uniformly mixed to form slurry.Appropriate slurry, which is dipped, with hairbrush is coated in commercially available ceramic tube
Outer surface, making it that the gold electrode of outer surface be completely covered, (internal diameter of tubular ceramic substrate is 0.7mm, outer diameter 1.1mm, length
For 4.5mm；Two cyclic annular gold electrodes being mutually parallel are come on its outer surface, the single width of two electrodes is 0.4mm, and spacing is
0.5mm；The platinum filament wire length drawn on gold electrode is 5mm)；
(8) coated ceramic tube at 300 DEG C is sintered 3h, ni-Cd heating coil is then passed through into Al2O3In ceramic tube
Portion passes to direct current to provide operating temperature.Ceramic tube is welded on general heater-type hexagonal tube socket finally by platinum filament wire
On, to obtain PdO@In2O3Base oxide semiconductor acetone sensor；
(9) finally by sensor in 300 DEG C of air environments aging 6 days, for use；
(10) sensitivity of the sensor to 100ppm acetone is tested at 250 DEG C.
Embodiment 3：
With three-dimensional counter opal PdO@In2O3Compound nano sensitive material makes acetone gas sensor, specific to make
It is as follows to make process：
(1) styrene of the kayexalate of 0.4g, the sodium bicarbonate of 0.35g, 40mL are added sequentially to first
In 400mL deionized waters, 70 DEG C of heating water baths and 1.2h is stirred under nitrogen atmosphere, the potassium peroxydisulfate of 0.3g is then added, after
Continuous 70 DEG C of heating water baths under nitrogen atmosphere simultaneously stir 20h；
(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 of 40mL, mass fraction 98%
In solution, after 40 DEG C of heating water bath stirring 5h, by alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then 80
It is dried at DEG C, obtains sulfonated polystyrene microsphere powder；
(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 in the 15mL deionized waters containing 0.161mL dilute hydrochloric acid and 0.15mL aqueous hydrogen peroxide solutions, stirs 60min
Until it is all dissolved；A concentration of 0.15M of dilute hydrochloric acid, the mass fraction of hydrogen peroxide is 30% in aqueous hydrogen peroxide solution；
(5) solution for obtaining step (4) ullrasonic spraying at 700 DEG C thermally decomposes 4h, in ullrasonic spraying pyrolysis
In the process always with nitrogen as carrier gas (nitrogen flow rate：400sccm), and in the taper of the tail portion of ullrasonic spraying thermal decomposer
Powder is collected in bottle.By alternately cleaning 6 times of obtained product deionized water and ethyl alcohol, then dried at 80 DEG C.Dry knot
Product is carried out calcining 3h by Shu Hou at 500 DEG C, to obtain three-dimensional counter opal structure In2O3Material, In2O3Material product
Quality is 80mg；
(6) the three-dimensional counter opal structure In for obtaining 30mg steps (5)2O3It is a concentration of that material is added to 5mL, palladium nitrate
Palladium nitrate (Pd (the NO of 20.8at.%3)2·2H2O it) is stirred in ethanol solution, is stirred to solution exsiccation；Finally, the powder that will be obtained
1h is calcined in end at 350 DEG C, to obtain three-dimensional counter opal structure PdO@In2O3Compound nano sensitive material PdO@In2O3
Material product quality is 25mg；
(7) PdO@In made from certain mass are taken2O3Compound nano sensitive material (sensitive material quality is 0.025mg)
With isopropanol 0.4mg in mass ratio:1mg is uniformly mixed to form slurry.Appropriate slurry, which is dipped, with hairbrush is coated in commercially available ceramic tube
Outer surface, making it that the gold electrode of outer surface be completely covered, (internal diameter of tubular ceramic substrate is 0.7mm, outer diameter 1.1mm, length
For 4.5mm；Two cyclic annular gold electrodes being mutually parallel are come on its outer surface, the single width of two electrodes is 0.4mm, and spacing is
0.5mm；The platinum filament wire length drawn on gold electrode is 5mm)；
(8) coated ceramic tube at 300 DEG C is sintered 3h, ni-Cd heating coil is then passed through into Al2O3In ceramic tube
Portion passes to direct current to provide operating temperature.Ceramic tube is welded on general heater-type hexagonal tube socket finally by platinum filament wire
On, to obtain PdO@In2O3Base oxide semiconductor acetone sensor；
(9) finally by sensor in 300 DEG C of air environments aging 6 days, for use；
(10) sensitivity of the sensor to 100ppm acetone is tested at 250 DEG C.
Claims (3)
1. one kind being based on three-dimensional counter opal structure PdO@In2O3The acetone gas sensor of compound nano sensitive material, for side
Hot type structure is carried the Al of two parallel, cyclic annular and separate gold electrodes by outer surface2O3Ceramic tube substrate is coated in pottery
Nano sensitive material on porcelain tube outer surface and gold electrode is formed with the ni-Cd heating coil being placed in ceramic tube；Its feature exists
In：Nano sensitive material is three-dimensional counter opal structure PdO@In2O3Compound, 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, under nitrogen atmosphere 40~80 DEG C of heating water baths and 0.5~1.5h of stirring,
Then the potassium peroxydisulfate of 0.05~0.35g is added, continue 40~80 DEG C of heating water baths under nitrogen atmosphere and stirs 15~20h；
(2) after reaction, product water and the ethyl alcohol alternately centrifuge washing that will be obtained, 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 40~80 DEG C of heating water baths stir 4~6h, obtained product deionized water and ethyl alcohol are alternately cleaned
It 5~7 times, is then dried at 70~90 DEG C, obtains sulfonated polystyrene microsphere powder；
(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 be added to containing 0.10~0.20mL dilute hydrochloric acid and 0.10~0.20mL aqueous hydrogen peroxide solutions 8~
In 20mL deionized waters, 40~80min of stirring is until it is all dissolved；A concentration of 0.1~0.2M of dilute hydrochloric acid, aquae hydrogenii dioxidi
The mass fraction of hydrogen peroxide is 25~30% in solution；
(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 is calcined at DEG C, to obtain three-dimensional counter opal structure In2O3Material；
(6) the three-dimensional counter opal structure In for obtaining 25~50mg steps (5)2O3Material is added to 3~6mL, palladium nitrate concentration
For the palladium nitrate (Pd (NO of 5.2~21at.%3)2·2H2O it) is stirred in ethanol solution, is stirred to solution exsiccation；Finally, it incites somebody to action
The powder arrived calcines 0.5~1.5h at 300~400 DEG C, to obtain three-dimensional counter opal structure PdO@In2O3Compound is received
Rice sensitive material.
2. described in claim 1 a kind of based on three-dimensional counter opal structure PdO@In2O3The acetone of compound nano sensitive material
The preparation method of gas sensor, its step are as follows：
(1) PdO@In are taken2O3Compound nano sensitive material and isopropanol in mass ratio 0.25~0.5:1 ratio is uniformly mixed
Form slurry；The Al that slurry coating carries two gold electrodes parallel, cyclic annular and separate on the surface is dipped with hairbrush2O3Pottery
Porcelain 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；
(3) coated ceramic tube is sintered to 2~5h at 200~350 DEG C, then adds the ni-Cd that resistance value is 30~40 Ω
Heat coil passes through Al2O3Ceramic tube inside passes to direct current to provide operating temperature, and operating temperature is 85~110 DEG C.Finally lead to
It crosses platinum filament wire ceramic tube is welded on general heater-type hexagonal tube socket；
(4) finally by sensor in 200~400 DEG C of air environments aging 5~7 days, to obtain three-dimensional counter opal structure
PdO@In2O3Oxide semiconductor acetone gas sensor.
3. as claimed in claim 2 a kind of based on three-dimensional counter opal structure PdO@In2O3The third of compound nano sensitive material
The preparation method of ketone gas sensor, it is characterised in that：Al2O3The internal diameter of ceramic tube be 0.6~0.8mm, outer diameter be 1.0~
1.5mm, length are 4~5mm；The width of single gold electrode 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, the length of 4~6mm.
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