CN109592713A - A kind of tungsten trioxide nano hollow sphere semiconductor material and preparation method thereof, a kind of gas sensor and its preparation method and application - Google Patents
A kind of tungsten trioxide nano hollow sphere semiconductor material and preparation method thereof, a kind of gas sensor and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of tungsten trioxide nano hollow sphere semiconductor material, belong to technical field of semiconductor, the present invention mixes soluble sexavalence tungsten salt, alcohol aqueous solvent and alkaline precipitating agent, gained mixed liquor is subjected to hydro-thermal reaction, obtains tungsten trioxide nano hollow sphere semiconductor material；The concentration of sexavalence tungsten salt is 5~30mmol/L in the mixed liquor, and the concentration of precipitating reagent is 0.1~0.5mol/L；The temperature of the hydro-thermal reaction is 100~200 DEG C, and the time of hydro-thermal reaction is 5~40h.The present invention obtains uniform particle diameter, crystal grain completely and the tungsten oxide nanometer hollow sphere semiconductor material of uniform wall thickness by the proportion and reaction temperature of control reaction raw materials and reaction time.The present invention also provides the gas sensors being prepared by above-mentioned tungsten trioxide nano hollow sphere semiconductor material, which are detected applied to organophosphorus insecticide, high sensitivity.
Description
Technical field
The present invention relates to technical field of semiconductor, in particular to a kind of tungsten trioxide nano hollow sphere semiconductor material
And preparation method thereof, a kind of gas sensor and its preparation method and application.
Background technique
Food safety is related to the public health problems such as human health, mainly exceeded by poisonous and harmful substance residual in food
Cause.In recent years, since planting environment pollution, pest and disease damage aggravation, the market demand increase and Pesticide use person lacks pesticide phase
Close professional knowledge etc., indiscriminate use of pesticide or unreasonable serious using phenomenon, so that Pesticide Residue, which becomes, causes food safety
One of main source of problem.Organophosphorus insecticide is that most widely used, usage amount is most in current agricultural products in China production process
Big a kind of pesticide.However, most of organophosphorus pesticide belongs to the pesticide of severe toxicity or hypertoxic type, have to the intracorporal cholinesterase of people
There is strong inhibiting effect, is easily entered in human body by modes such as mucous membrane, alimentary canal, respiratory tract, oral cavities, intrusion human consumption system
System, the circulatory system and nervous system, the Functional tissues such as heart, liver, the kidney of Injuries and poisoning person take in organophosphorus pesticide
Exceeded food can seriously affect human body health.There are many type of organophosphorus pesticide, and representative organophosphorus pesticide has: acetyl
Acephatemet, DDVP, parathion and parathion-methyl etc..The common detection method of organophosphorus pesticide residue is main at present
Have: chromatography, mass spectrography and chromatograph-mass spectrometer coupling method etc..But these methods want the professional knowledge attainment of reviewer
Ask height, time and effort consuming, test result analysis method complicated, related experimental facilities is expensive and analysis real-time is low, mostly only
Suitable for laboratory testing, it is difficult to realize that real-time live detects.Therefore increasingly serious Pesticide Residue is faced, one kind is studied
Accurately and reliably, method that is effective, convenient and efficient, being applicable in Detecting Pesticide on site is most important.
In recent years, metal oxide semiconductor sensor as it is a kind of prepare it is simple, cheap and with long service life
Semiconductor transducer is widely used in fields such as industrial production, environmental monitoring and human lives.WO3Nanometer material
Material shows a series of new because having quantum size effect, small-size effect, skin effect and macro quanta tunnel effect
The light of surprise, heat, electricity, sound, magnetic characteristic, are widely studied and are applied in terms of the research of semiconductor transducer sensitive material.
In the prior art, WO is prepared3The method of hollow ball-shape structural material has template, sol-gel method etc., but these methods are both needed to
A large amount of strong acid and organic solvent are introduced, it is at high cost, pollution environment is easily caused, and WO is prepared3Hollow ball-shape structural material
Pattern it is unstable.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of tungsten trioxide nano hollow sphere semiconductor material and its preparation sides
Method, a kind of gas sensor extremely preparation method, the preparation of tungsten trioxide nano hollow sphere semiconductor material provided by the invention
A large amount of strong acid, raw material be simple and easy to get, at low cost and tungsten trioxide nano hollow sphere semiconductor material obtained without introducing for method
Uniform particle diameter, crystal grain is complete and uniform wall thickness, is passed by the air-sensitive that the tungsten trioxide nano hollow sphere semiconductor material is prepared
Sensor is detected for organophosphorus insecticide, high sensitivity.
The present invention provides a kind of preparation methods of tungsten trioxide nano hollow sphere semiconductor material, comprising the following steps:
Soluble sexavalence tungsten salt, alcohol aqueous solvent and alkaline precipitating agent are mixed, gained mixed liquor row hydro-thermal reaction obtains
Tungsten trioxide nano hollow sphere semiconductor material；
The concentration of sexavalence tungsten salt is 5~30mmol/L in the mixed liquor, the concentration of alkaline precipitating agent is 0.1~
0.5mol/L；
The temperature of the hydro-thermal reaction is 100~200 DEG C, and the time of hydro-thermal reaction is 5~40h.
Preferably, the water soluble hexavalent tungsten salt is WCl6、Na2WO4·2H2O or Na2WO4。
Preferably, the alcohol aqueous solvent be small molecule alcohol solvent and water mixture, the small molecule alcohol solvent and
The volume ratio of water is 30~50:100.
Preferably, the small molecule alcohol solvent includes one or more of methanol, ethyl alcohol and propyl alcohol.
Preferably, the alkaline precipitating agent is urea, thiocarbamide or ammonium hydroxide.
It is described the present invention also provides the tungsten trioxide nano hollow sphere semiconductor material that above-mentioned preparation method is prepared
The partial size of tungsten trioxide nano hollow sphere is 350~500nm, and wall thickness is 20~40nm.
The present invention also provides a kind of preparation methods of gas sensor, comprising the following steps:
1) tungsten trioxide nano hollow sphere semiconductor material is mixed with adhesive, gained paste is coated on ceramic tube
Outer surface obtains the ceramic tube with wet coating；The tungsten trioxide nano hollow sphere semiconductor material is above-mentioned preparation method
The tungsten trioxide nano hollow sphere semiconductor material being prepared；
2) ceramic tube for having wet coating in the step 1) is successively dried and is calcined, obtain the ceramics with dry coating
Pipe；
3) by the step 2) have dry coating ceramic tube 4 wire electrodes be welded on pedestal, by heater strip from
It is passed through in ceramic tube with dry coating and its both ends is welded on pedestal, gained element is subjected to aging, obtain air-sensitive biography
Sensor.
Preferably, the temperature calcined in the step 2) is 250~350 DEG C, and the time of calcining is 2~5h.
The present invention also provides the gas sensors that above-mentioned preparation method is prepared.
The gas sensor being prepared the present invention also provides above-mentioned preparation method is in organophosphorus insecticide context of detection
Application.
Advantageous effects: the present invention provides a kind of preparation method of tungsten trioxide nano hollow sphere semiconductor material,
Soluble sexavalence tungsten salt, alcohol aqueous solvent and alkaline precipitating agent are mixed, by gained mixed liquor row hydro-thermal reaction, obtain tungstic acid
Nano-hollow ball semiconductor material；The concentration of sexavalence tungsten salt is 5~30mmol/L, the concentration of alkaline precipitating agent in the mixed liquor
For 0.1~0.5mol/L；The temperature of the hydro-thermal reaction is 100~200 DEG C, and the time of hydro-thermal reaction is 5~40h.The present invention
It can obtain that uniform particle diameter, crystal grain are complete and wall thickness is equal by controlling proportion and reaction temperature and the reaction time of reaction raw materials
Even tungsten oxide nanometer hollow sphere semiconductor material.
The present invention also provides the gas sensor being prepared by above-mentioned tungsten trioxide nano hollow sphere semiconductor material,
The gas sensor is detected applied to organophosphorus insecticide, high sensitivity.
Detailed description of the invention:
Fig. 1 is the WO being prepared in embodiment 23The X ray diffracting spectrum of hollow sphere nano material；
Fig. 2 is the WO being prepared in 1~embodiment of embodiment 33Nano-hollow ball semiconductor material scanning electron microscopy
The SEM photograph of mirror；
Fig. 3 is the WO being prepared in 1~embodiment of embodiment 33Nano-hollow ball semiconductor material transmission electron microscopy
The TEM photo of mirror；
Fig. 4 is the relational graph that the voltage for the gas sensor that embodiment 6 obtains changes with orthene concentration；
Fig. 5 is the response recovery curve of the gas sensor arrived prepared in embodiment 6；
Fig. 6 is that WO is based in embodiment 73Response diagram of the nano-hollow ball sensor to different material；
Fig. 7 is the SEM photograph of WO3 nano-hollow ball semiconductor material scanning electron microscope obtained in embodiment 4；
Fig. 8 is the SEM photograph of WO3 nano-hollow ball semiconductor material scanning electron microscope obtained in embodiment 5.
Specific embodiment
The present invention provides a kind of preparation methods of tungsten trioxide nano hollow sphere semiconductor material, comprising the following steps:
Soluble sexavalence tungsten salt, alcohol aqueous solvent and alkaline precipitating agent are mixed, gained mixed liquor row hydro-thermal reaction obtains
Tungsten trioxide nano hollow sphere semiconductor material；
The concentration of sexavalence tungsten salt is 5~30mmol/L in the mixed liquor, the concentration of alkaline precipitating agent is 0.1~
0.5mol/L；
The temperature of the hydro-thermal reaction is 100~200 DEG C, and the time of hydro-thermal reaction is 5~40h.
In the present invention, the water soluble hexavalent tungsten salt is preferably WCl6、Na2WO4·2H2O or Na2WO4。
In the present invention, described to state the mixture that alcohol aqueous solvent is preferably small molecule alcohol solvent and water, the small molecule
The volume ratio of alcohols solvent and water is preferably 30~50:100, more preferably 35~45:100.
In the present invention, the small molecule alcohol solvent preferably includes one or more of methanol, ethyl alcohol and propyl alcohol, more
Preferably ethyl alcohol.When small molecule alcohol solvent is two or more small molecular alcohol, dosage of the present invention to small molecular alcohol
Than being not particularly limited, mixed with arbitrary proportion.
In the present invention, the alkaline precipitating agent is preferably urea, thiocarbamide or ammonium hydroxide.
In the present invention, the soluble sexavalence tungsten salt, alcohol aqueous solvent and the method for alkaline precipitating agent mixing are preferably first
It is stirred after soluble sexavalence tungsten salt is mixed with alcohol aqueous solvent, then adds alkaline precipitating agent.
In the present invention, the time of the stirring is preferably 5~10min, and the present invention does not have special limit to the method for stirring
It is fixed, select stirring means well known to those skilled in the art.The present invention keeps soluble sexavalence tungsten salt completely molten by stirring
In alcohol aqueous solvent.
In the present invention, the concentration of sexavalence tungsten salt is 5~30mmol/L, preferably 10~25mmol/ in the mixed liquor
L, more preferably 15~20mmol/L；The concentration of the mixed liquor neutral and alkali precipitating reagent be 0.1~0.5mol/L, preferably 0.2
~0.3mol/L.In the present invention, with the increase of reactant concentration, the hollow spheres uniformity increases, partial size and wall thickness increase
Greatly.
In the present invention, the temperature of the hydro-thermal reaction is 100~200 DEG C, is selected as 100~150 DEG C, more preferably 110
~130 DEG C；The time of the hydro-thermal reaction is 5~40h, preferably 10~30h, more preferably 15~20h.In the present invention,
The hydrothermal temperature is excessively high, and products therefrom is easily reunited, and the too low products therefrom of reaction temperature is difficult to form hollow structure；
With the growth of the hydro-thermal reaction time, significant changes do not occur for the partial size of gained tungsten trioxide nano hollow sphere, but shell thickness reduces,
Granulation uniformity is deteriorated.
It in the present invention, further preferably include that gained reaction solution is successively cooled to room temperature, is centrifuged, is washed after the hydro-thermal reaction
It washs and dries, obtain tungsten trioxide nano hollow sphere semiconductor material.
The present invention is not particularly limited the rate being cooled to room temperature, and selects rate well known to those skilled in the art i.e.
It can；The present invention is not particularly limited the method for centrifugation, selects centrifugal method well known to those skilled in the art, can make solid-liquid
Separation.
In the present invention, the washing preferably successively carries out ethanol washing and washing to obtained solid product after centrifugation.
The present invention is not particularly limited ethanol washing and the method for washing, selects washing methods well known to those skilled in the art i.e.
It can.
In the present invention, the drying is preferably dried obtained solid product after washing.In the present invention, described
Dry temperature is preferably 50~100 DEG C, and more preferably 70~80 DEG C；The time of the drying is preferably 12~20h, more preferably
For 16~18h.
The present invention provides the tungsten trioxide nano hollow sphere semiconductor material that above-mentioned preparation method is prepared, described three
The partial size of tungsten oxide nanometer hollow sphere is 350-500nm, and wall thickness is 20~40nm.
The present invention also provides a kind of preparation methods of gas sensor, comprising the following steps:
1) tungsten trioxide nano hollow sphere semiconductor material is mixed with adhesive, gained paste is coated on ceramic tube
Outer surface obtains the ceramic tube with wet coating；The tungsten trioxide nano hollow sphere semiconductor material is above-mentioned preparation method
The tungsten trioxide nano hollow sphere semiconductor material being prepared；
2) ceramic tube for having wet coating in the step 1) is successively dried and is calcined, obtain the ceramics with dry coating
Pipe；
3) by the step 2) have dry coating ceramic tube 4 wire electrodes be welded on pedestal, by heater strip from
It is passed through in ceramic tube with dry coating and its both ends is welded on pedestal, gained element is subjected to aging, obtain air-sensitive biography
Sensor.
The present invention mixes tungsten trioxide nano hollow sphere semiconductor material with adhesive, and gained paste is coated on pottery
Porcelain tube outer surface obtains the ceramic tube with wet coating；The tungsten trioxide nano hollow sphere semiconductor material is above-mentioned three oxygen
Change the tungsten oxide that preparation method described in tungsten nano-hollow ball semiconductor material or claim 2~6 any one is prepared
Nano-hollow ball semiconductor material.
In the present invention, the tungsten trioxide nano hollow sphere semiconductor material is preferably ground.The present invention is to grinding
Method be not particularly limited, select grinding method well known to those skilled in the art.In the present invention, it is preferred in Ma
It is ground in Nao mortar, the present invention is not particularly limited milling time, makes tungsten trioxide nano hollow sphere semiconductor material
It is uniformly dispersed.
In the present invention, described adhesive is preferably water, terpinol, carboxymethyl cellulose, more preferably water；The bonding
The dosage of agent is preferably the 10~50% of tungsten trioxide nano hollow sphere semiconductor material quality, and more preferably 25%.The present invention
The method mixed to tungsten trioxide nano hollow sphere semiconductor material with adhesive is not particularly limited, and selects those skilled in the art
Mixed method known to member.
In the present invention, the ceramic tube is preferably the ceramic tube with Pt lead and Au electrode.
In the present invention, the paste is not particularly limited in the coating thickness of ceramic tube outer surface, selects this field
The arbitrarily well known coating thickness of technology.
After obtaining the ceramic tube with wet coating, the ceramic tube with wet coating is successively dried and is calcined by the present invention, is obtained
To the ceramic tube for having dry coating.
In the present invention, the drying is preferably infrared drying.Be particularly preferred as will the ceramic tube with wet coating it is vertical with
It is dried under infrared lamp in ceramic Noah's ark.
In the present invention, the temperature of the calcining is preferably 250~350 DEG C, and more preferably 300~320 DEG C, the calcining
Time be preferably 2~5h, more preferably 3~4h.The present invention removes adhesive by calcining, and material tight is made to be coated in pottery
Porcelain tube surface forms dense material coating.
After obtaining the ceramic tube of dry coating, 4 wire electrodes of the ceramic tube with dry coating are welded on pedestal by the present invention
Above, heater strip is passed through from the ceramic tube with dry coating and its both ends is welded on pedestal, gained element carried out old
Change, obtains gas sensor.
In the present invention, the pedestal is preferably the mating pedestal of air-sensitive beta version；The time of the aging is preferably 3~10
It, more preferably 5~7 days.
The present invention also provides the gas sensors that above-mentioned preparation method is prepared.
The gas sensor being prepared the present invention also provides above-mentioned preparation method is in organophosphorus insecticide context of detection
Application.
In the present invention, the organophosphorus insecticide is preferably orthene, DDVP, Rogor or parathion, more excellent
It is selected as orthene.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1:
By the WCl of 0.72mmol660mL alcohol-water (V is addedEthyl alcohol/VWater: 30%) in solution.It is placed on magnetic stirring apparatus and stirs
After mixing 5min, slightly white translucent solution is obtained；It is then transferred to 100mL polytetrafluoroethyllining lining stainless steel cauldron
In, while 0.1g urea is added and obtains mixed liquor.WCl in gained mixed liquor6Concentration be 12mmol/L.
For 24 hours as hydro-thermal reaction in 120 DEG C of electric dry oven by reaction kettle, cooled to room temperature；It is white by being collected by centrifugation
Color product, and washed respectively with deionization ethyl alcohol and deionized water, it is then dried overnight at 80 DEG C, obtains WO3Nano-hollow ball
Semiconductor material.
Embodiment 2:
WCl in gained mixed liquor6Concentration be 16mmol/L, it is other identical as condition in embodiment 1.
Embodiment 3
WCl in gained mixed liquor6Concentration be 20mmol/L, it is other identical as condition in embodiment 1.
Fig. 1 is the WO being prepared in embodiment 23The X ray diffracting spectrum of hollow sphere nano material, in figure labelled in
All XRD diffraction maximums and standard diagram (JCPDS No.46-1096,) the completely consistent cubic phase of belonging in peak
WO3, occur in figure without obvious other impurity peaks, illustrate that sample is single WO3Phase.
Fig. 2 is the WO being prepared in 1~embodiment of embodiment 33Nano-hollow ball semiconductor material scanning electron microscopy
The SEM photograph of mirror, wherein 2a, 2b, 2c are respectively embodiment 1, WO obtained in embodiment 2 and embodiment 33Nano-hollow ball half
The SEM photograph of conductor scanning of materials electron microscope.As shown in Figure 2, with WCl6Concentration be sequentially increased,
Fig. 3 is the WO being prepared in 1~embodiment of embodiment 33Nano-hollow ball semiconductor material transmission electron microscopy
The TEM photo of mirror；Wherein 3a, 3b, 3c are respectively embodiment 1, WO obtained in embodiment 2 and embodiment 33Nano-hollow ball half
The TEM photo of conductor material transmission electron microscope.
By Fig. 2 and Fig. 3 it is found that working as WCl6Concentration be 16mmol/L when, synthesized WO3Nano material all has sky
Bulbus cordis shape regular morphology, grain size is consistent and uniform wall thickness.Therefore, by controlling WCl6Concentration can control WO3Nanometer is empty
Pattern, particle size distribution and the Thickness Distribution of bulbus cordis.
Embodiment 4
The temperature of hydro-thermal reaction is 150 DEG C.It is other same as Example 2.Fig. 7 is WO obtained in embodiment 43Nanometer is empty
The SEM photograph of bulbus cordis semiconductor material scanning electron microscope, it is synthesized when the temperature of hydro-thermal reaction is 150 DEG C as shown in Figure 7
WO3, by being declined, and there is slight agglomeration compared with embodiment 2 in nano-hollow ball even particle size degree.
Embodiment 5
The time of hydro-thermal reaction is 36h.It is other same as Example 2.Fig. 8 is WO obtained in embodiment 53Nano-hollow
The SEM photograph of ball semiconductor material scanning electron microscope, it is synthesized when the time of hydro-thermal reaction is 36h as shown in Figure 8
WO3The nano-hollow ball nano particle uniformity is declined, and part spherical shell fracture phenomena occurs.
Embodiment 6
WO prepared by merging embodiment 1 in the agate mortar3Nano-hollow ball semiconductor material 100mg, after grinding uniformly
50mg binder is instilled, is tuned into after paste and is uniformly applied to bamboo stick outside ceramic tube, WO will be coated with3Nano-hollow ball semiconductor material
The ceramic tube of material, which is stood in ceramic Noah's ark, to be placed under infrared lamp after drying, 300 DEG C of calcining 3h in Muffle furnace, to remove in material
Binder used, it is spare after natural cooling.4 wire electrodes of the ceramic tube obtained after calcining are welded on pedestal, then
By heater strip from being passed through in ceramic tube and its both ends being also welded on pedestal, gas sensor is made, gas sensor is placed in specially
On agingtable, aging 240h obtains gas sensor.
Fig. 4 is the relational graph that the voltage for the gas sensor that the present embodiment obtains changes with orthene concentration.By Fig. 4
Know that the voltage for the gas sensor that the present embodiment obtains increases with orthene concentration and increased, it is in a linear relationship.
Fig. 5 is the response recovery curve of the gas sensor arrived prepared in the present embodiment.Define response time tresFor member
After part contacts tested gas, load resistance RLOn voltage by U0Change to U0+ 90% (UX-U0) needed for time, recovery time
trevAfter being detached from tested gas for gas sensor, load resistance RLVoltage by UXIt is restored to U0+ 10% (UX-U0) used in when
Between.From figure 5 it can be seen that the gas sensor that the present embodiment obtains has preferable response to the orthene of 1ppm, and
The response-recovery time is short, respectively 13s and 10s.
Embodiment 7
Using the WO prepared in embodiment 63Nano-hollow ball sensor detects four kinds of common organophosphorus insecticides, mistake
Journey and steps are as follows:
Using static volumetric method, the WO that embodiment 6 is prepared on HW-30A Testing system of gas-sensor built3Nanometer is empty
Bulbus cordis sensor carries out gas sensor performance test.The important technological parameters of test macro are as follows: TCH test channel number: 30 tunnels；Acquisition
Speed, 1 time/s；System composition error, 1%；Power supply, 220V, 50Hz；Heating voltage Vh, 5V；Loop voltage Vc, 5V；Load electricity
Hinder RL.Pass through test and the concatenated load resistance R of gas sensorLOn voltage Vout reflect the characteristic of gas sensor.Most
It is respectively 25ppm DDVP to concentration to test macro, orthene, parathion-methyl, right at 290 DEG C of good operating temperature
Sulphur phosphorus, isopropanol, formaldehyde, acetone and ammonia carry out air-sensitive test.
Fig. 6 is to be prepared in the present embodiment based on WO3Nano-hollow ball sensor to orthene, DDVP, Rogor,
Parathion, isopropanol, formaldehyde, eight kinds of substances of acetone and ammonia response diagram, wherein DDVP, Rogor, parathion and acetyl
Acephatemet is four kinds of relatively conventional at present organophosphorus insecticides.Define element sensitivity S=Ra/Rg, Ra and Rg be respectively
Element in air with the voltage value in tested gas.By 6 figures it is found that under the conditions of operating temperature is 290 DEG C, the gas sensor
It is good compared with other toxic and harmful gas to the response of organophosphorus insecticide, wherein it is best to orthene response, illustrate it to second
The selectivity of acyl acephatemet is strong.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of tungsten trioxide nano hollow sphere semiconductor material, comprising the following steps:
Soluble sexavalence tungsten salt, alcohol aqueous solvent and alkaline precipitating agent are mixed, by gained mixed liquor row hydro-thermal reaction, obtain three oxygen
Change tungsten nano-hollow ball semiconductor material；
The concentration of sexavalence tungsten salt is 5~30mmol/L in the mixed liquor, and the concentration of alkaline precipitating agent is 0.1~0.5mol/L；
The temperature of the hydro-thermal reaction is 100~200 DEG C, and the time of hydro-thermal reaction is 5~40h.
2. preparation method according to claim 1, which is characterized in that the water soluble hexavalent tungsten salt is WCl6、Na2WO4·
2H2O or Na2WO4。
3. preparation method according to claim 1, which is characterized in that the alcohol aqueous solvent is small molecule alcohol solvent and water
Mixture, the volume ratio of the small molecule alcohol solvent and water is 30~50:100.
4. according to the method described in claim 3, it is characterized in that, the small molecule alcohol solvent includes methanol, ethyl alcohol and third
One or more of alcohol.
5. preparation method according to claim 1, which is characterized in that the alkaline precipitating agent is urea, thiocarbamide or ammonium hydroxide.
6. the tungsten oxide nanometer hollow sphere that preparation method described in Claims 1 to 5 any one is prepared, feature exist
In the partial size of the tungsten trioxide nano hollow sphere is 350~500nm, and wall thickness is 20~40nm.
7. a kind of preparation method of gas sensor, comprising the following steps:
1) tungsten trioxide nano hollow sphere semiconductor material is mixed with adhesive, gained paste is coated on ceramic tube appearance
Face obtains the ceramic tube with wet coating；The tungsten trioxide nano hollow sphere semiconductor material is that Claims 1 to 5 is any
The tungsten trioxide nano hollow sphere semiconductor material that preparation method described in one is prepared；
2) ceramic tube for having wet coating in the step 1) is successively dried and is calcined, obtain the ceramic tube with dry coating；
3) 4 wire electrodes that the ceramic tube of dry coating is had in the step 2) are welded on pedestal, by heater strip from having
It is passed through in the ceramic tube of dry coating and its both ends is welded on pedestal, gained element is subjected to aging, obtains gas sensor.
8. preparation method according to claim 7, which is characterized in that the temperature calcined in the step 2) is 250~350
DEG C, the time of calcining is 2~5h.
9. the gas sensor that preparation method described in claim 7~8 any one is prepared.
10. the gas sensor that preparation method described in claim 7~8 any one is prepared is examined in organophosphorus insecticide
Survey the application of aspect.
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