CN110243879A - A kind of SnO of sulphion modification2Base low temperature SO2Sensitive material and preparation method thereof - Google Patents
A kind of SnO of sulphion modification2Base low temperature SO2Sensitive material and preparation method thereof Download PDFInfo
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- CN110243879A CN110243879A CN201910571527.2A CN201910571527A CN110243879A CN 110243879 A CN110243879 A CN 110243879A CN 201910571527 A CN201910571527 A CN 201910571527A CN 110243879 A CN110243879 A CN 110243879A
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The present invention provides a kind of sulphion surface modification SnO2Prepare low temperature SO2The synthetic method of sensitive material, the present invention are prepared for SnO2 nano particle first with sol-gel method.Prepared SnO2Partial size (10~20nm) and preferable dispersibility of the nano particle with very little.Later in this patent to prepared nano SnO2Surface modification is carried out.Using hydro-thermal method in SnO2Nano grain surface carries out sulphion doping, is prepared for the SnO of sulphion surface modification2Base sensitive material.It can be realized to SO2Low temperature detection, optimum detection temperature is by pure SnO2280 DEG C be reduced to 180 DEG C.And it improves to SO2The response of gas shows preferable stability and response-recovery characteristic.
Description
Technical field
The invention belongs to metal-oxide semiconductor (MOS) base gas sensors and environmental monitoring technology field, and in particular to a kind of
The SnO of sulphion modification2Base low temperature SO2Sensitive material and sensor and preparation method thereof.
Background technique
Along with the propulsion of World Modern process of industrialization, environmental pollution is more seriously people's asking of having to face
Topic.In the production process in the fields such as chemical industry, coal, petroleum, natural gas, carbon monoxide, hydrogen sulfide, sulfur dioxide etc. is inflammable,
Explosive, toxic gas leakage can cause extreme influence to environment and safety in production.Fire, poisoning for occurring in daily life etc.
Also all there is direct relationship with the leakage of these gases.The harm for caused by how reducing these gases, in addition to control
Outside the discharge for reducing gas, should also these gases be carried out with monitoring accurately and quickly.So gas sensor is in this respect
It has broad application prospects.
SnO2A kind of important semiconductor functional material, to the research of stannic oxide mainly explore its air-sensitive performance,
The application of catalytic performance related fields.Nano SnO2Material can all show gas-sensitive property to a variety of gases, work as nano-silica
When change tin is leaked in gas with various cruelly, different variations can occur for resistance value.Such as in SO2In equal reducibility gas, dioxy
The resistance for changing tin reduces.It is generally believed that how much related, Lacking oxygens of the air-sensitive performance of nano tin dioxide material and its Lacking oxygen
More, air-sensitive performance is better.Certain air-sensitive performance also with operating temperature, material particle size, the type of dopant and concentration and gas
The manufacturing process of quick element etc. is related.
Although pure nano-stannic oxide is to SO2Gas shows certain response, but its response is lower, and best sound
It answers temperature higher, is unfavorable for application of the sensing element in real life.To SnO2Nano material, which is doped, obviously to be changed
It is apt to its sensitive property.In document before, people mainly have studied SnO2Cation doping, including precious metal doping (platinum,
Palladium, gold and silver etc.) and metal oxide semiconductor doping (for example, zinc oxide, manganese oxide, ceria and four oxidation three
Cobalt etc.).But to SnO2It is less that nano material carries out anion doped research.It is using first in some documents seldom at present
It prepares stannic disulfide, then by stannic disulfide partial oxidation is SnO2Method, prepare stannic disulfide doping SnO2Base sensitivity material
Material.But the problems such as pattern and partial size of stannic disulfide existing for the method cannot control well.
Summary of the invention
Based on background above and there are the problem of, the method comprises the steps of firstly, preparing nano SnOs2Material, prepared SnO2Have
The partial size of very little and good dispersibility.And on this basis proposition hydro-thermal method to SnO2Sulphion surface modification has been carried out,
The SO of prepared sulphion modification2Base sensitive material can be realized to SO2The low temperature of gas detects, and its response relative to
Pure SnO2To SO2Response it is high.
In order to toxic gas SO2It is more accurately and rapidly detected, this patent research is prepared for nano SnO2Air-sensitive
Material, and carried out sulphion modification on this basis and be prepared for low temperature SO2Sensitive material.It is being used for SO2It is showed when detection
High response, good selectivity, stability and response-recovery characteristic out.
The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of SnO of sulphion modification2Base low temperature SO2Sensitive material, the SO2Sensitive material
Including SnO2Nano particle and be located at the SnO2The SnS of nano grain surface2, the sulphion is with SnS2Form deposit
It is SnO2Nano grain surface；The SnS2With SnO2Molar ratio be 0.03~0.05:1.
Based on above technical scheme, it is preferred that the SnO2The size of nano particle is 10~20nm.
Another aspect of the present invention provides a kind of SnO of above-mentioned sulphion modification2Base low temperature SO2The preparation method of sensitive material,
SnO is prepared using sol-gel method2After nano particle, then use hydro-thermal method using thioacetamide to SnO2Nano particle carries out
Sulphion modification in surface obtains a kind of SnO of surface sulphion modification2Nano particle, as SO2Sensitive material.
Based on above technical scheme, it is preferred that the sol-gel method prepares SnO2The process of nano particle is will
SnCl4·5H2O, after ethylenediamine tetra-acetic acid and deionized water 1:0.1~0.3:15 in mass ratio are mixed.In magnetic agitation and 70
Under DEG C water bath condition, ammonium hydroxide is added dropwise dropwise thereto to pH value of solution=3~7.After solution cooling and standings, time of repose preferably 3
It, precipitation and separation washs drying, and 400~600 DEG C of 2~4h of oxidizing roasting obtain SnO2Nano material；The sulphion is repaired
Decorations process is using hydro-thermal method to SnO2It is surface-treated.By SnO2Nano particle, glacial acetic acid and thioacetamide are in mass ratio
1:4:5~10 are add to deionized water, wherein SnO2The concentration of nano particle is 0.01g/ml, is obtained after stirring 20~40min
To mixed liquor, by after the sealing of this mixed liquor at 120~200 DEG C 10~20h of isothermal reaction.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Nano particle.
Based on above technical scheme, it is preferred that the hydro-thermal reaction is carried out in autoclave, with 2.5 DEG C/min's
Heating rate is heated to required temperature.
Based on above technical scheme, it is preferred that the washing process is all to be washed respectively with deionized water and dehydrated alcohol
It washs precipitating each three times.
Based on above technical scheme, it is preferred that the drying process is carried out at 80~120 DEG C, drying time
All it is 8~15h, is vacuum drying.
Based on above technical scheme, it is preferred that the mass fraction of the described dropwise addition ammonium hydroxide is 10%, ammonium hydroxide dropwise addition be using
Dropping funel is added dropwise.
Based on above technical scheme, it is preferred that the oxidizing roasting process is carried out in Muffle furnace, with 5 DEG C/min
Heating rate be heated to required temperature.
Further aspect of the present invention provides a kind of low temperature SO2Gas sensor, the sensor include sensing element and sensitivity
Material；The sensitive material is the SnO of above-mentioned sulphion modification2Base low temperature SO2Sensitive material；The sensing element of the sensor
Composition it is identical as the general sensing element composition of existing gas sensor, the sensor is tubular structure；With aluminium oxide sky
Heart ceramic tube is main element, coats gold thread circle on ceramic tube in advance, and two platinum electrodes of adhesion respectively, later with sulphur from
The SnO of son modification2Be that gas sensitive is coated on ceramic pipe surface, and using nichrome wire be adding thermal resistance across ceramic tube as
Heating element.
Based on above technical scheme, it is preferred that the ceramic pipe diameter about 1.2~1.8mm, long 5~7mm, thickness of pipe wall
0.3~0.5mm.
Based on above technical scheme, it is preferred that the resistance value of the adding thermal resistance is 25~28 Ω.
The present invention also provides a kind of SnO of above-mentioned sulphion modification2Base low temperature SO2The preparation method of gas sensor, system
Preparation Method is as follows,
1. preparing the SnO of sulphion modification2Base low temperature SO2Sensitive material
2. the SnO that above-mentioned sulphion is modified2Base low temperature SO2Sensitive material and deionized water, deionized water and alcohol press matter
Amount is mixed than 1:0.5:0.5, and slurry is made in grinding, and slurry is coated uniformly on ceramic pipe surface, welds working electrode after drying
It connects on sensing element pedestal, while being also welded on sensing element pedestal after resistive heater is passed through ceramic tube, obtain SO2Gas
Body sensor.
Nano SnO is prepared using sol-gel method the present invention relates to a kind of2Basis material, and sulphur is carried out on this basis
Ion surface modification prepares low temperature SO2The method of sensitive material, has the advantage that
Beneficial effect
1. the surfactant when present invention uses ethylenediamine tetra-acetic acid to prepare stannic oxide as sol-gel method, made
Standby product has lesser granularity, preferable dispersibility.
2. the present invention proposes to use sulphion surface modification SnO2Method prepare SO2Sensitive material, prepared material can
Realize SO2Low temperature detection.
3. in the present invention after surface modification through sulphion, SnO2The resistance of sensitive material significantly reduces, this is in practical application
In can be effectively reduced the energy consumption of sensor.
4. SnO prepared by the present invention2Basis material has the partial size of very little, and favorable dispersibility, to SO2Show compared with
High response.
5. a kind of SnO of sulphion modification prepared by the present invention2Base low temperature SO2Sensitive material can be realized to sulfur dioxide
Low temperature, quickly, the detection of high response, have broad application prospects.
Detailed description of the invention
Fig. 1 is SnO prepared by embodiment 22Transmission electron microscope (TEM) figure of nano material；
Fig. 2 is SO 2 sensor in the embodiment of the present invention 2 at different temperatures to the SO of 500ppm2The sound of gas
Answer curve.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.1:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 2
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
The SnO prepared in Fig. 1 embodiment of the present invention2The partial size of nano particle is 10~20nm or so, and particle dispersion
Preferably, even particle size.
The SnO of the sulphion surface modification prepared in Fig. 2 embodiment of the present invention 22Sensor and SnO2Sensor is in not equality of temperature
To the SO of 500ppm under degree2The response curve of gas, response S is defined as: S=Ra/Rg, RaAnd RgRespectively sensor is in air
Resistance value when neutralizing in certain density sulfur dioxide gas between two platinum electrodes, it can be seen from the figure that sulphion surface is repaired
The SnO of decorations2Base low temperature SO2Gas sensor performance is substantially better than pure SnO2Sensor (without sulphion surface modification).
Embodiment 3
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.3:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 4
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=3.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 5
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=7.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；By sensitive material, deionized water and alcohol in mass ratio 1:
0.5:0.5 mixing, grinding are made slurry and are coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature
SO2Gas sensor.
Embodiment 6
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 400 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 7
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 600 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 8
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 2h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 9
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 4h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 10
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:5 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 11
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:10 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 12
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 120 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 13
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 200 DEG C isothermal reaction 15h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 14
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 10h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Embodiment 15
The SnO of sulphion surface modification2Base low temperature SO2Gas sensor
By SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.2:15 in mass ratio are mixed, wherein SnCl4·
5H2The additional amount of O is 10g.Under magnetic agitation and 70 DEG C of water bath conditions, ammonium hydroxide is added dropwise dropwise to pH value of solution=5.Solution is cold
But after standing, precipitation and separation washs drying, and 500 DEG C of oxidizing roasting 3h obtain SnO2Nano material；By SnO2Nano particle, ice
Acetic acid and thioacetamide 1:4:8 in mass ratio are added in 80g deionized water, wherein SnO2The additional amount of nano particle is
After 1g, magnetic agitation 30min, by this mixed liquor sealing after at 160 DEG C isothermal reaction 20h.Precipitation and separation later washs drying
The SnO of sulphion surface modification is obtained afterwards2Base SO2Sensitive material；1g sensitive material, 0.5g deionized water and 0.5g alcohol are mixed
It closes, grinding is made slurry and is coated uniformly on ceramic pipe surface, and electrode welding is carried out after drying and obtains low temperature SO2Gas sensing
Device.
Claims (10)
1. a kind of SO2Sensitive material, which is characterized in that the SO2Sensitive material includes SnO2Nano particle and be located at the SnO2
The SnS of nano grain surface2；The SnS2With SnO2Molar ratio be 0.03~0.05:1.
2. SO according to claim 12Sensitive material, which is characterized in that the SnO2The size of nano particle be 10~
20nm。
3. SO described in a kind of claim 12The preparation method of sensitive material, which is characterized in that prepare SnO with sol-gel method2
After nano particle, then use hydro-thermal method using thioacetamide to SnO2Nano particle carries out the modification of surface sulphion, obtains institute
State the SnO of sulphion modification2Base low temperature SO2Sensitive material.
4. preparation method according to claim 3, which is characterized in that described method includes following steps:
(1) sol-gel method prepares SnO2: by SnCl4·5H2O, ethylenediamine tetra-acetic acid and deionized water 1:0.1 in mass ratio
After~0.3:15 mixing, after 60~80 DEG C of stirring in water bath, dropwise addition ammonium hydroxide to pH value of solution=3~7, after solution cooling and standings,
Precipitation and separation washs drying in 400~600 DEG C of 2~4h of oxidizing roasting and obtains SnO2Nano particle；
(2) using hydro-thermal method to SnO2Nano particle is surface-treated: by SnO2Nano particle, glacial acetic acid and thioacetamide
1:4:5~10 are add to deionized water in mass ratio, wherein SnO2The concentration of nano particle be 0.01g/ml, stirring 20~
Mixed liquor is obtained after 40min, by 10~20h of isothermal reaction, precipitation and separation are washed at 120~200 DEG C after mixed liquor sealing
The SnO of the sulphion modification is obtained after washing drying2Base low temperature SO2Sensitive material.
5. preparation method according to claim 3, which is characterized in that the mass fraction of the dropwise addition ammonium hydroxide is 10%；
The mass fraction of the glacial acetic acid is 98%.
6. preparation method according to claim 3, which is characterized in that the drying is vacuum drying, and drying temperature is
80-120 DEG C, drying time is 8~15h.
7. preparation method according to claim 3, which is characterized in that the oxidizing roasting process be in Muffle furnace into
Row, is heated to required temperature with the heating rate of 5 DEG C/min.
8. preparation method according to claim 3, which is characterized in that the hydro-thermal reaction is carried out in autoclave,
100~200 DEG C are heated to the heating rate of 2.5 DEG C/min.
9. a kind of low temperature SO2Gas sensor, the sensor include sensing element and sensitive material, which is characterized in that described quick
Sense material is SO of any of claims 1 or 22Sensitive material.
10. low temperature SO described in a kind of claim 92The preparation method of gas sensor, which is characterized in that the method includes such as
Lower step:
(1) SnO for modifying the sulphion2Base low temperature SO2Sensitive material, deionized water and alcohol 1:0.5:0.5 in mass ratio
Slurry is made in mixing, grinding；
(2) slurry is coated on sensing element, obtains the low temperature SO2Gas sensor.
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