CN109655499A - A kind of gas sensitive and preparation method thereof for nitrogen dioxide sensor - Google Patents
A kind of gas sensitive and preparation method thereof for nitrogen dioxide sensor Download PDFInfo
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Abstract
The invention discloses a kind of gas sensitives for nitrogen dioxide sensor, it is combined by stannic oxide and four three tin two-phases of oxidation, have stannic oxide-four and aoxidizes three tin nano composite structures, the microcosmic upper three-dimensional hierarchical structure to be assembled by the zero dimension particle of stannic oxide and four three tin of oxidation.Provided by the present invention for the gas sensitive of nitrogen dioxide sensor, has very high sensitivity, lower Nitrogen dioxide testing limit to nitrogen dioxide, nitrogen dioxide has faster response and resume speed, has extraordinary selectivity to nitrogen dioxide gas.
Description
Technical field
The present invention relates to gas sensor technical field, in particular to a kind of gas sensitive for nitrogen dioxide sensor
And preparation method thereof.
Background technique
Nitrogen oxide is one of main pollutant in air, including many oxide, wherein most importantly NO and
NO2.Nitrogen oxides can be dissolved in water and form nitric acid, lead to the formation of acid rain；The effect of the ingredients such as nitrogen oxides and ammonia, moisture can produce
Secondary aerosol species pollution produces the photochemistry secondary pollutions such as ozone with volatile organic matter under the conditions ofs high temperature, sunshine etc.；
Nitrogen oxides is that the photochemically reactive main producers object of ozone occurs, and can generate nitrate by a series of photochemical reaction
Aerosol leads to acid deposition, city On The Deterioration of Visibility Over, gray haze phenomenon etc. occurs；It can be to human body in addition, being directly sucked in nitrogen oxides
Various organs, especially respiratory system generate directly harm, cause respiratory disease etc..According to standard GB/T 3095-
2012, NO in surrounding air2Year, day and a hour concentration limit value be respectively 40,80,200 μ g/m3, be roughly equal to 21.2,42.4,
106 ppb.It is seriously threatened it can be seen that nitrogen oxides causes atmospheric environment and human health, it is effectively detected
Have great importance with monitoring to environment protection and people's health.
The advantages that metal oxide sensor is at low cost since its structure is simple, and the service life is long, high sensitivity is led in air-sensitive
Domain has been widely used.But existing nitrogen dioxide sensor is low to nitrogen dioxide sensitivity, detection limit for height, selectivity compared with
Difference, influences that nitrogen dioxide is qualitative and the accuracy of quantitative detection result.
Summary of the invention
It is an object of the invention to overcome the shortcomings of that the above-mentioned detection sensitivity in the presence of the prior art is low, one kind is provided
Gas sensitive and preparation method thereof for nitrogen dioxide sensor.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes:
A kind of gas sensitive for nitrogen dioxide sensor is combined by stannic oxide and four three tin two-phases of oxidation, is had
Stannic oxide-four aoxidizes three tin nano composite structures, microcosmic upper for by the zero dimension particle assembling of stannic oxide and four three tin of oxidation
Made of three-dimensional hierarchical structure.
The above-mentioned gas sensitive for nitrogen dioxide sensor has three-dimensional manometer composite construction, and large specific surface area can
Gas sensitive is improved to the responsiveness of nitrogen dioxide, gas sensitive is made to have very high sensitivity to nitrogen dioxide；Due to above-mentioned
Gas sensitive is also very prominent to the response of low concentration nitrogen dioxide to the high sensitivity of nitrogen dioxide, therefore has lower
Detection limit；Above-mentioned gas sensitive has three-dimensional manometer composite construction, has a large amount of hole in material, is conducive to titanium dioxide nitrogen
The diffusion of body molecule, therefore above-mentioned gas sensitive has faster response and resume speed to nitrogen dioxide；- four oxygen of stannic oxide
Changing three tin structures has good compatibility to nitrogen dioxide, but poor to other reducibility gas compatibilities, therefore above-mentioned gas
Quick material has extraordinary selectivity to nitrogen dioxide gas.
Further, the gas sensitive is prepared through hydro-thermal or solvent-thermal method, is then calcined and is obtained in atmospheric conditions.
The present invention also provides a kind of preparation method of above-mentioned gas sensitive for nitrogen dioxide sensor, including it is as follows
Step:
1) solvent is mixed with tin source, acid-base modifier and surfactant, and 6~48h of insulation reaction at 150~220 DEG C；
Preferably, the insulation reaction temperature is 180 DEG C, and the insulation reaction time is 12h；
2) precipitation and separation after step 1) insulation reaction obtains powder after cleaned, dry；
3) powder that step 2 obtains is under atmospheric conditions, and 400~700 DEG C of 0.5~5h of calcining are to get the gas sensitive；
Preferably, the calcination temperature is 600 DEG C, calcination time 2h.
Above-mentioned preparation method first generates precipitating using hydrothermal/solvent thermal method, then calcines gained precipitating in atmospheric conditions
Gas sensitive provided by the invention can be prepared, required equipment is simple, and process is mature, and it is low in cost, be conducive to air-sensitive material
The cost control of material and a wide range of popularization and use.
Preferably, solvent described in step 1) is the water perhaps composition of ethyl alcohol or water and ethyl alcohol.
It is further preferred that the volume ratio of composition of the solvent described in step 1) for water and ethyl alcohol, water and ethyl alcohol is (1:7)
~(1:0).
It is further preferred that the volume ratio of water and ethyl alcohol is (1:3)~(1:0) in solvent described in step 1).
It is highly preferred that the volume ratio of water and ethyl alcohol is 3:5 in solvent described in step 1).
Further, the concentration of tin source in a solvent is 0.02~0.5mol/L in step 1).
Preferably, the concentration of tin source in a solvent is 0.05~0.15mol/L in step 1).
Preferably, the concentration of tin source in a solvent is 0.1mol/L in step 1).
Further, the ratio between tin source, acid-base modifier described in step 1) and the amount of substance of surfactant are 1:(0.5
~2): (0.5~3).
Preferably, the ratio between tin source, acid-base modifier described in step 1) and the amount of substance of surfactant be 1:(1~
1.5): (0.5~1).
It is highly preferred that the ratio between tin source, acid-base modifier described in step 1) and the amount of substance of surfactant are 1:1:
0.5。
Preferably, the tin source is the composition of one or more of stannous chloride, stannous sulfate and stannous fluoride；Institute
Stating acid-base modifier is inorganic acid highly basic；The surfactant is sodium citrate, in cetyl trimethylammonium bromide
One or two kinds of compositions.Illustratively, the inorganic acid highly basic can be the common strong acid such as sodium hydroxide, hydrogen chloride
Or highly basic.
Preferably, cleaning described in step 2 refers to is cleaned with water and ethyl alcohol, and wash number is no less than 4 times.Preferably, it cleans
Number is 6 times.The drying refers in 70 DEG C of dry 10h.
The present invention also provides a kind of nitrogen dioxide sensor, the sensor surface is coated with above-mentioned gas sensitive, institute
State gas sensitive coating with a thickness of 5~300 μm.The coating procedure are as follows: take a small amount of gas sensitive to mix with solvent, grinding is equal
It is even to paste, be then coated in sensor consumptive material surface to obtain the final product.The nitrogen dioxide sensor need to be in 100~350 DEG C after being made
It could be used with enhancing its stability within aging at least 7 days.Solvent used in coating procedure can for water, ethyl alcohol, petroleum ether,
The common solvents such as hexamethylene, coating method can be manual application or mechanical coating.
The sensor consumptive material is commercial consumptive material, mainly there is plane formula, tubular type and MEMS formula, mainly include measuring electrode,
Heater strip or heating electrode and bracket etc..
Above-mentioned nitrogen dioxide sensor belongs to metal oxide sensor, has structure simple, and at low cost, the service life is long, spirit
The advantages that sensitivity is high, is particularly suitable for a wide range of detection of nitrogen dioxide gas concentration, and scene is used in gas concentration alarm etc..
The present invention also provides above-mentioned nitrogen dioxide sensor nitrogen dioxide measured either qualitatively or quantitatively or nitrogen dioxide is dense
Purposes in degree alarm.
By using above-mentioned technical proposal, the invention has the following beneficial effects:
1) provided by the present invention for the gas sensitive of nitrogen dioxide sensor, there is three-dimensional manometer composite construction, specific surface area
Greatly, it can be improved gas sensitive to the responsiveness of nitrogen dioxide, gas sensitive made to have very high sensitivity to nitrogen dioxide；By
It is also very prominent to the response of low concentration nitrogen dioxide in the gas sensitive to the high sensitivity of nitrogen dioxide, thus have compared with
Low Nitrogen dioxide testing limit；The gas sensitive has three-dimensional manometer composite construction, has a large amount of hole in material, is conducive to
The diffusion of nitrogen dioxide gas molecule, therefore the gas sensitive has faster response and resume speed to nitrogen dioxide；Dioxy
Changing the three tin structures of oxidation of tin-four has good compatibility to nitrogen dioxide, but poor to other reducibility gas compatibilities, because
This gas sensitive has extraordinary selectivity to nitrogen dioxide gas.
2) above-mentioned preparation method provided by the invention first generates precipitating using hydrothermal/solvent thermal method, then in atmospheric conditions
Precipitating obtained by lower calcining can prepare gas sensitive provided by the invention, and required equipment is simple, and process is mature, at low cost
It is honest and clean, be conducive to the cost control and a wide range of popularization and use of gas sensitive.
3) nitrogen dioxide sensor provided by the invention belongs to metal oxide sensor, has structure simple, at low cost,
The advantages that service life is long, high sensitivity, is particularly suitable for a wide range of detection of nitrogen dioxide gas concentration, and gas concentration alarm etc. is used
Scene.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the gas sensitive provided by the invention with nano composite structure.
Specific embodiment
Below with reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
It is all that this is belonged to based on the technology that the content of present invention is realized for the scope of the above subject matter of the present invention is limited to the following embodiments
The range of invention.
Embodiment 1
In the preparation process of a certain sensing material, sensing material is prepared using solvent-thermal method.Solvent for use is 15mL high purity water
With the mixture of 25mL dehydrated alcohol, tin source used is 4mmol stannous chloride, and acid-base modifier is 4mmol sodium hydroxide, surface
Activating agent is 2mmol sodium citrate.It after above-mentioned substance is mixed and stirred for 30 min, is transferred in the reaction kettle of 50mL, in 180
12h is kept the temperature in DEG C baking oven, is then cooled to room temperature.Then precipitated product is centrifuged and is cleaned, respectively using high-purity
Water and ethyl alcohol carry out eccentric cleaning, amount to 6 times, and completion is placed in 70 DEG C of baking ovens dry 10h.After the completion of drying place the material in
In porcelain boat, in being calcined in tube furnace, calcination temperature is 600 DEG C, calcination time 2h.It is cooled to room temperature after the completion of calcining,
A small amount of material is taken, takes water as a solvent and is volatilized completely coated on flat surface sensor consumptive material to solvent with mortar grinder to paste
Afterwards, by sensor aging 7 days under the conditions of 150 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor.
The sensor is to NO2Has excellent sensitivity, to the NO of 5,10,20,50 ppm2Response be respectively
240,440,660 and 950.Meanwhile the response of the NO2 of 50 ppb can easily detected there is still 2.5, it can
See that the sensor has very low detection to NO2 and limits.Its to 100 ppm ethyl alcohol, acetone, toluene response be only 16,5.3,
2.0, it is seen that it has excellent NO2Selectivity.Its NO to 20 ppm2Response and recovery time be only 30 s and 15 s, tool
Standby faster response and resume speed.
Embodiment 2
In the preparation process of a certain sensing material, sensing material is prepared using solvent-thermal method.Solvent for use is 40mL high purity water,
Tin source used is 4mmol stannous sulfate, and acid-base modifier is 4mmol potassium hydroxide, and surfactant is 10mmol cetyl
Trimethylammonium bromide.It after above-mentioned substance is mixed and stirred for 60min, is transferred in the reaction kettle of 50mL, is protected in 200 DEG C of baking ovens
Warm 18h, then cools to room temperature.Then worth product is centrifuged and is cleaned, uses high purity water and ethyl alcohol respectively
Eccentric cleaning is carried out, is amounted to 4 times, completion is placed in 70 DEG C of baking ovens dry 10h.Place the material in porcelain boat after the completion of drying,
In being calcined in tube furnace, calcination temperature is 500 DEG C, calcination time 5h.It is cooled to room temperature after the completion of calcining, takes a small amount of material
Material, taking water as a solvent after solvent volatilizees completely, will be sensed with mortar grinder to paste coated on flat surface sensor consumptive material
For device aging 9 days under the conditions of 200 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor.
The sensor is to NO2Has excellent sensitivity, to the NO of 1,5,10 ppm2Response be 38,164 respectively
With 230.It is only 9.0,2.4,5.2 to the response of 100 ppm ethyl alcohol, acetone, toluene, it is seen that it has excellent NO2Choosing
Selecting property.It is only 20 s and 14 s to the response of 20 ppmNO2 and recovery time, has faster response and resume speed.
Embodiment 3
In the preparation process of a certain sensing material, sensing material is prepared using solvent-thermal method.Solvent for use be 5mL high purity water and
The mixture of 35mL dehydrated alcohol, tin source used are 4mmol stannous fluoride, and acid-base modifier is 4mmol sodium hydroxide, and surface is living
Property agent be 4mmol sodium citrate.It after above-mentioned substance is mixed and stirred for 60 min, is transferred in reaction kettle, in 220 DEG C of baking ovens
8h is kept the temperature, is then cooled to room temperature.Then precipitated product is centrifuged and is cleaned, respectively using high purity water and ethyl alcohol into
Row eccentric cleaning amounts to 5 times, and completion is placed in 70 DEG C of baking ovens dry 10h.Place the material in porcelain boat after the completion of drying, in
It is calcined in tube furnace, calcination temperature is 700 DEG C, calcination time 1.5h.It is cooled to room temperature after the completion of calcining, takes a small amount of material
Material, taking water as a solvent after solvent volatilizees completely, will be sensed with mortar grinder to paste coated on flat surface sensor consumptive material
For device aging 7 days under the conditions of 200 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor.
The sensor is to NO2Has excellent sensitivity, to the NO of 5,10,20,50 ppm2Response be respectively
162,369,580 and 852.It is only 11,4.1,3.4 to the response of 100 ppm ethyl alcohol, acetone, toluene, it is seen that it has excellent
Different NO2Selectivity.Its NO to 20 ppm2Response and recovery time be only 25 s and 16 s, have faster response and extensive
Complex velocity.
Experimental example 1
Response of the gas sensitive and existing some gas sensitives of measurement Examples 1 to 3 preparation to nitrogen dioxide gas respectively
Value, measurement result are as shown in the table:
As can be seen from the above table, provided by the present invention for the gas sensitive of nitrogen dioxide sensor, to the dioxy of same concentrations
The response for changing nitrogen is much larger than other gas sensitives, and it is very high to illustrate that gas sensitive provided by the invention has nitrogen dioxide
Sensitivity；Meanwhile gas sensitive provided by the invention most low energy detects that concentration is the nitrogen dioxide of 50ppb, illustrates this hair
The gas sensitive of bright offer has lower detection to nitrogen dioxide gas and limits.
Experimental example 2
Sensing material is prepared using solvent-thermal method, tin source is stannous chloride, and acid-base modifier is sodium hydroxide, and surfactant is
Sodium citrate, the ratio between fixed stannous chloride, amount of substance of sodium hydroxide and sodium citrate are 1:1:0.5, accordingly change chlorination
The additional amount of stannous, sodium hydroxide and sodium citrate prepares nitrogen dioxide sensor of the invention, and measures it and be to concentration
The response of the nitrogen dioxide gas of 5ppm.
Solvent for use is the mixture of 15mL high purity water and 25mL dehydrated alcohol, stannous chloride, sodium hydroxide and citric acid
The dosage of sodium is as shown in table 1.It after above-mentioned substance is mixed and stirred for 30 min respectively, is transferred in the reaction kettle of 50mL, in 180
12h is kept the temperature in DEG C baking oven, is then cooled to room temperature.Then precipitated product is centrifuged and is cleaned, respectively using high-purity
Water and ethyl alcohol carry out eccentric cleaning, amount to 6 times, and completion is placed in 70 DEG C of baking ovens dry 10h.After the completion of drying place the material in
In porcelain boat, in being calcined in tube furnace, calcination temperature is 600 DEG C, calcination time 2h.It is cooled to room temperature after the completion of calcining,
A small amount of material is taken, takes water as a solvent and is volatilized completely coated on flat surface sensor consumptive material to solvent with mortar grinder to paste
Afterwards, by sensor aging 7 days under the conditions of 150 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor.
Each experimental group solute dosage of table 1
The response measurement result of nitrogen dioxide gas of the nitrogen dioxide sensor of each experimental group preparation to concentration for 5ppm is such as
Shown in table 2.
Response of each experimental group nitrogen dioxide sensor of table 2 to the nitrogen dioxide gas that concentration is 5ppm
As can be seen from the above table: the sound of nitrogen dioxide sensor prepared by experimental group one to the nitrogen dioxide gas that concentration is 5ppm
Response highest should be worth；From experimental group one to four as can be seen that when tin source concentration is gradually decreased from 0.1mol/L, gas obtained
Quick material gradually decreases the response of nitrogen dioxide gas, and when tin source concentration is 0.01mol/L, gas sensitive obtained is to two
The response of nitrogen oxide gas is lower than 100；From experimental group one, five, six and seven as can be seen that when tin source concentration from 0.1mol/L by
When edging up high, gas sensitive obtained gradually decreases the response of nitrogen dioxide gas, when tin source concentration is 0.5mol/L, system
The gas sensitive obtained is lower than 100 to the response of nitrogen dioxide gas.
Above-mentioned description of test, in preparation method of the present invention, when tin source concentration is 0.02~0.5mol/L, the air-sensitive of preparation
Material is more preferable to the sensitivity of nitrogen dioxide gas；When tin source concentration is 0.1mol/L, the gas sensitive of preparation is to titanium dioxide
The sensitivity of nitrogen is best.
Experimental example 3
Sensing material is prepared using solvent-thermal method, tin source is stannous chloride, and acid-base modifier is sodium hydroxide, and surfactant is
Sodium citrate, fixed solvent and stannous chloride dosage, change the additional amount of sodium hydroxide and sodium citrate, prepare of the invention two
Nitrogen oxide sensor, and measure its response to the nitrogen dioxide gas that concentration is 5ppm.
Solvent for use is the mixture of 15mL high purity water and 25mL dehydrated alcohol, stannous chloride, sodium hydroxide and citric acid
The dosage of sodium is as shown in table 3.It after above-mentioned substance is mixed and stirred for 30 min respectively, is transferred in the reaction kettle of 50mL, in 180
12h is kept the temperature in DEG C baking oven, is then cooled to room temperature.Then precipitated product is centrifuged and is cleaned, respectively using high-purity
Water and ethyl alcohol carry out eccentric cleaning, amount to 6 times, and completion is placed in 70 DEG C of baking ovens dry 10h.After the completion of drying place the material in
In porcelain boat, in being calcined in tube furnace, calcination temperature is 600 DEG C, calcination time 2h.It is cooled to room temperature after the completion of calcining,
A small amount of material is taken, takes water as a solvent and is volatilized completely coated on flat surface sensor consumptive material to solvent with mortar grinder to paste
Afterwards, by sensor aging 7 days under the conditions of 150 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor.
Each experimental group sodium hydroxide of table 3 and sodium citrate dosage
| Experimental group | Stannous chloride, mmol | Sodium hydroxide, mmol | Sodium citrate, mmol | The ratio between amount of solute substance |
| Experimental group one | 4 | 4 | 2 | 1:1:0.5 |
| Experimental group two | 4 | 2 | 2 | 1:0.5:0.5 |
| Experimental group three | 4 | 8 | 2 | 1:2:1 |
| Experimental group four | 4 | 4 | 4 | 1:1:1 |
| Experimental group five | 4 | 4 | 8 | 1:1:2 |
| Experimental group six | 4 | 4 | 12 | 1:1:3 |
The response measurement result of nitrogen dioxide gas of the nitrogen dioxide sensor of each experimental group preparation to concentration for 5ppm is such as
Shown in table 4.
Response of each experimental group nitrogen dioxide sensor of table 4 to the nitrogen dioxide gas that concentration is 5ppm
| Experimental group | Response |
| Experimental group one | 240 |
| Experimental group two | 202 |
| Experimental group three | 123 |
| Experimental group four | 185 |
| Experimental group five | 165 |
| Experimental group six | 93 |
As can be seen from the above table: the sound of nitrogen dioxide sensor prepared by experimental group one to the nitrogen dioxide gas that concentration is 5ppm
Response highest should be worth；The sound of nitrogen dioxide sensor prepared by experimental group two to five to the nitrogen dioxide gas that concentration is 5ppm
It should be worth and be in higher range；The nitrogen dioxide gas that nitrogen dioxide sensor prepared by experimental group six is 5ppm to concentration
Response response it is lower.
Above-mentioned description of test, in preparation method of the present invention, tin source, the optimisation substance of acid-base modifier and surfactant
The ratio between amount is 1:1:0.5；When the ratio between amount of substance of tin source, acid-base modifier and surfactant is 1:(0.5~2): (0.5
~3) when, the gas sensitive of preparation is good to the sensitivity of nitrogen dioxide gas.
Experimental example 4
Sensing material is prepared using solvent-thermal method.Solvent for use is the mixture of 15mL high purity water and 25mL dehydrated alcohol, used
Tin source is 4mmol stannous chloride, and acid-base modifier is 4mmol sodium hydroxide, and surfactant is 2mmol sodium citrate.It will be upper
After stating material mixing and stirring 30 min, it is transferred in the reaction kettle of 50mL, 12h is kept the temperature in baking oven, then cool to room temperature.
Holding temperature is as shown in table 5 in each experimental group baking oven.Then precipitated product is centrifuged and is cleaned, respectively using high-purity
Water and ethyl alcohol carry out eccentric cleaning, amount to 6 times, and completion is placed in 70 DEG C of baking ovens dry 10h.After the completion of drying place the material in
In porcelain boat, in being calcined in tube furnace, calcination temperature is 600 DEG C, calcination time 2h.It is cooled to room temperature after the completion of calcining,
A small amount of material is taken, takes water as a solvent and is volatilized completely coated on flat surface sensor consumptive material to solvent with mortar grinder to paste
Afterwards, by sensor aging 7 days under the conditions of 150 DEG C, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor is surveyed
Its fixed response to the nitrogen dioxide gas that concentration is 5ppm.
Holding temperature and soaking time in each experimental group baking oven of table 5
| Experimental group | Holding temperature, DEG C | Soaking time, h |
| Experimental group one | 180 | 12 |
| Experimental group two | 160 | 12 |
| Experimental group three | 150 | 12 |
| Experimental group four | 140 | 12 |
| Experimental group five | 190 | 12 |
| Experimental group six | 200 | 12 |
| Experimental group seven | 220 | 12 |
The response measurement result of nitrogen dioxide gas of the nitrogen dioxide sensor of each experimental group preparation to concentration for 5ppm is such as
Shown in table 6.
Response of each experimental group nitrogen dioxide sensor of table 6 to the nitrogen dioxide gas that concentration is 5ppm
| Experimental group | Response |
| Experimental group one | 240 |
| Experimental group two | 211 |
| Experimental group three | 146 |
| Experimental group four | 132 |
| Experimental group five | 169 |
| Experimental group six | 87 |
| Experimental group seven | 74 |
As can be seen from the above table: the sound of nitrogen dioxide sensor prepared by experimental group one to the nitrogen dioxide gas that concentration is 5ppm
Response highest should be worth；The sound of nitrogen dioxide sensor prepared by experimental group two to five to the nitrogen dioxide gas that concentration is 5ppm
It should be worth and be in higher range；Nitrogen dioxide sensor prepared by experimental group six and experimental group seven is to two that concentration is 5ppm
The response response of nitrogen oxide gas is lower.
Above-mentioned description of test, in preparation method of the present invention, the optimum temperature of insulation reaction is 180 DEG C, best soaking time
For 12h.
Experimental example 5
Sensing material is prepared using solvent-thermal method.Solvent for use is the mixture of 15mL high purity water and 25mL dehydrated alcohol, used
Tin source is 4mmol stannous chloride, and acid-base modifier is 4mmol sodium hydroxide, and surfactant is 2mmol sodium citrate.It will be upper
After stating material mixing and stirring 30 min, it is transferred in the reaction kettle of 50mL, keeps the temperature 12h in 180 DEG C of baking ovens, be subsequently cooled to
Room temperature.Then precipitated product is centrifuged and is cleaned, carries out eccentric cleaning using high purity water and ethyl alcohol respectively, amounts to 6
Secondary, completion is placed in 70 DEG C of baking ovens dry 10h.Place the material in porcelain boat after the completion of drying, in calcining 2h in tube furnace.Respectively
Calcination temperature and calcination time are as shown in table 7 in experimental group.It is cooled to room temperature after the completion of calcining, takes a small amount of material, be molten with water
Agent mortar grinder is coated on flat surface sensor consumptive material, to paste after solvent volatilizees completely, by sensor in 150 DEG C of items
Aging 7 days under part, that is, obtaining has SnO2-Sn3O4The NO of nano composite structure2Sensor measures it to two that concentration is 5ppm
The response of nitrogen oxide gas.
Each experimental group calcination temperature of table 7 and calcination time
| Experimental group | Holding temperature, DEG C | Calcination time, h |
| Experimental group one | 600 | 2 |
| Experimental group two | 500 | 2 |
| Experimental group three | 400 | 2 |
| Experimental group four | 300 | 2 |
| Experimental group five | 700 | 2 |
| Experimental group six | 800 | 2 |
The response measurement result of nitrogen dioxide gas of the nitrogen dioxide sensor of each experimental group preparation to concentration for 5ppm is such as
Shown in table 8.
Response of each experimental group nitrogen dioxide sensor of table 8 to the nitrogen dioxide gas that concentration is 5ppm
| Experimental group | Response |
| Experimental group one | 240 |
| Experimental group two | 156 |
| Experimental group three | 123 |
| Experimental group four | 102 |
| Experimental group five | 97 |
| Experimental group six | 26 |
As can be seen from the above table: the sound of nitrogen dioxide sensor prepared by experimental group one to the nitrogen dioxide gas that concentration is 5ppm
Response highest should be worth；The sound of nitrogen dioxide sensor prepared by experimental group two to four to the nitrogen dioxide gas that concentration is 5ppm
It should be worth and be in higher range；The nitrogen dioxide that nitrogen dioxide sensor prepared by experimental group five and six is 5ppm to concentration
The response of gas is lower.
Above-mentioned description of test, in preparation method of the present invention, the optimum temperature of calcining is 600 DEG C, and the Best Times of calcining are
2h。
Claims (10)
1. a kind of gas sensitive for nitrogen dioxide sensor, which is characterized in that the gas sensitive is by stannic oxide and four
Aoxidize three tin two-phases to be combined, have stannic oxide-four and aoxidize three tin nano composite structures, it is microcosmic it is upper for by stannic oxide with
The three-dimensional hierarchical structure that the zero dimension particle of four three tin of oxidation assembles.
2. being used for the gas sensitive of nitrogen dioxide sensor as described in claim 1, which is characterized in that the gas sensitive warp
Hydro-thermal or solvent-thermal method preparation, then calcine in atmospheric conditions and obtain.
3. the preparation method of the gas sensitive of any of claims 1 or 2 for nitrogen dioxide sensor, which is characterized in that packet
It includes following steps: 1) mixing solvent with tin source, acid-base modifier and surfactant, and kept the temperature instead at 150~220 DEG C
Answer 6~48h；2) precipitation and separation after step 1) insulation reaction obtains powder after cleaned, dry；3) step 2 obtains
Powder under atmospheric conditions, 400~700 DEG C of 0.5~5h of calcining are to get the gas sensitive.
4. preparation method as claimed in claim 3, which is characterized in that solvent described in step 1) is water or ethyl alcohol, Huo Zheshui
With the composition of ethyl alcohol.
5. preparation method as claimed in claim 3, which is characterized in that in step 1) the concentration of tin source in a solvent be 0.02~
0.5mol/L。
6. preparation method as claimed in claim 5, which is characterized in that in step 1), the tin source, acid-base modifier and surface
The ratio between amount of substance of activating agent is 1:(0.5~2): (0.5~3).
7. preparation method as claimed in claim 3, which is characterized in that the tin source is stannous chloride, stannous sulfate and fluorination
The composition of one or more of stannous；The acid-base modifier is inorganic acid highly basic；The surfactant is lemon
The composition of one or both of sour sodium, cetyl trimethylammonium bromide.
8. preparation method as claimed in claim 3, which is characterized in that cleaning refers to described in step 2 is cleaned with water and ethyl alcohol,
Wash number is no less than 4 times.
9. a kind of nitrogen dioxide sensor, which is characterized in that the sensor surface is coated with gas of any of claims 1 or 2
Quick material, the gas sensitive coating with a thickness of 5~300 μm.
10. nitrogen dioxide sensor as claimed in claim 9 nitrogen dioxide measured either qualitatively or quantitatively or content of nitrogen dioxide report
Purposes in police.
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