CN104990959B - A kind of preparation method of copper and the compound hydrogen sulfide gas sensitive of tin oxide - Google Patents
A kind of preparation method of copper and the compound hydrogen sulfide gas sensitive of tin oxide Download PDFInfo
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- CN104990959B CN104990959B CN201510405767.7A CN201510405767A CN104990959B CN 104990959 B CN104990959 B CN 104990959B CN 201510405767 A CN201510405767 A CN 201510405767A CN 104990959 B CN104990959 B CN 104990959B
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Abstract
The present invention relates to a kind of preparation methods to toxic and harmful gas hydrogen sulfide with the copper of good response and selectivity and the composite air-sensitive material of tin oxide.By controlling the mass ratio of raw material copper source and stannous source in reaction, a step solvent-thermal method is utilized to obtain the composite air-sensitive material of copper and tin oxide.The composite air-sensitive material of copper and tin oxide in the air-sensitive test result display present invention shows good selectivity and response to toxic and harmful gas hydrogen sulfide, and response temperature is at 120 DEG C and to other gases almost without response.The present invention has the characteristics that preparation is simple and product property is good so that the composite air-sensitive material of the copper and tin oxide has good application prospect in gas sensor field, can reduce cost to the greatest extent in actual production and guarantee personal safety.
Description
Technical field
The invention belongs to metal oxide semiconductor sensor material preparation process technical fields, belong to composite semiconductor gas
Quick material is conducive to improve performance.
Background technology
Stannic oxide is one of the semiconductor gas sensor material studied earliest.In the development course of its decades,
The advantages that good conductivity, crystal structure and applicability, makes it in semiconductor gas sensor field, is always to study and answer
Hot spot.And selectivity is strong, stability is good, high sensitivity, of low cost, air-sensitive operating temperature reduce as possible and simple in structure
It is the indispensable demand of gas sensitive development.In practical application, increase the surface area and surface defect of stannic oxide nano material, it can be with
Make its ambient enviroment that can generate strong influence to its photoelectric property and air-sensitive performance, but pure tin dioxide gas-sensitive material is responding
Property and selectivity on disadvantage it is still very important, so add suitable additive be improve air-sensitive performance effective way it
One.It is reported with SnO currently, having lot of documents research2It is tested for the doping of sill.Such as：Mix different cations
Dopant, such as Sb, Pd, In, Ag etc. or anion doped doses of F and B.The experimental results showed that reasonable doping system appropriate
SnO can be significantly improved2Air-sensitive performance and photoelectric properties.But the doping system research of Cu is at present still mainly with gas sensing property and conduction
Based on Journal of Sex Research, the influence research to the variation of the micro-structure, pattern of such doping system to its air-sensitive performance is relatively fewer.
So oxide semiconductor gas sensor material in majority of case mixed with noble metal catalyst, such as platinum（Pt）, palladium（Pd）With
Gold（Au）Deng.But the load of this noble metal is not only of high cost but also environmental pollution is serious.
Invention content
In order to overcome the deficiencies of the prior art, the present invention provides a kind of system of copper and the compound hydrogen sulfide gas sensitive of tin oxide
Preparation Method, Semiconductor gas sensors material prepared by the present invention are applicable to manufacture stink damp dependent sensor.
A kind of preparation method of copper and the compound hydrogen sulfide gas sensitive of tin oxide, the gas sensitive are copper simple substance and oxidation
The composite material of tin, pattern are rounded bulbous, and size is within 300nm, which is characterized in that preparation method includes following step
Suddenly：
（1）It is raw material to weigh copper source that mass ratio is 10-20% and stannous source, is added in beaker and is stirred with deionized water magnetic force
It mixes to be completely dissolved to solution and clarify；Weigh the polyvinylpyrrolidone of the oxalic acid and 2% solvent quality of the amount in 10 times of stannous sources mole
（K=30）It is added, magnetic agitation is dissolved to solution secondary clearing again；Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method,
200 DEG C of constant temperature keep the temperature 12h；
（2）After the completion of reaction, centrifuges and wash collection product；Absolute ethyl alcohol is added to be ground to the product that experiment is collected into
Even paste is coated on gold electrode alumina ceramic tube, gas sensor has been prepared；
Step（1）In copper source be can be dissolved in deionized water at room temperature and discharge copper ion in water, stannous source is
Deionized water can be dissolved at room temperature and discharge stannous ion in water.
Step（1）In the unlimited duration of magnetic agitation, final reaction solution clarification.
Step（1）The filling rate of middle hydrothermal reaction kettle is equal to or less than 60%.
Step（2）The preparation of middle gas sensor is using conventional heater-type method for manufacturing gas sensor.
The advantage of the invention is that：The preparation method simple possible of this experiment, simple process and low cost is honest and clean, only passes through control
The mass ratio in copper source and stannous processed source, one step hydro thermal method can be obtained by the copper for having good selectivity and responsiveness to hydrogen sulfide
With tin oxide composite air-sensitive material.Resulting materials size uniform, diameter is within 300nm, and subsequent air-sensitive test result table
The bright present invention is suitable for the preparation of hydrogen sulfide semiconductor gas sensor.
Description of the drawings
Fig. 1 is that copper and the XRD x ray diffraction spectrograms of tin dioxide composite material is made in embodiment 2；
Fig. 2 is that copper and the scanning electron microscope diagram of tin dioxide composite material is made in embodiment 2（50000 times）；
Fig. 3 is that copper and the scanning electron microscope diagram of tin dioxide composite material is made in embodiment 2（200000 times）；
Fig. 4 be embodiment 2 be made copper and tin dioxide composite material at different temperatures to the H of 10ppm2S's is sensitive
Degree；
Fig. 5 is the spirit at 120 DEG C to the gas with various of 10ppm that copper and tin dioxide composite material is made in embodiment 2
Sensitivity.
Specific implementation mode
Embodiment 1：
（1）It is raw material that electronic balance, which weighs the copper source that mass ratio is 10% and chlorine stannous source, is added in beaker and uses deionized water
Magnetic agitation is completely dissolved to solution and clarifies.
（2）Weigh the polyvinylpyrrolidone of the oxalic acid and 2% solvent quality of the amount in 10 times of stannous sources mole（K=30）It is added
（1）In middle beaker, magnetic agitation is dissolved to solution secondary clearing again.
（3）Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method, and 200 DEG C of constant temperature keep the temperature 12h.
（4）After the completion of reaction, product is collected by centrifugation in washing three times respectively for deionized water and alcohol.
（5）It is prepared by heater-type gas sensor：Add absolute ethyl alcohol to be ground to uniform paste the product that experiment is collected into, uses
Fine, soft fur pen is coated in on gold electrode alumina ceramic tube.After ceramic tube welding encapsulation, the aging 5 on 4.5V agingtables
It, has been prepared gas sensor.Air-sensitive test is completed on WS-30A, and uses the hydrogen sulfide gas of 10% concentration in the process.
Embodiment 2：
（1）It is raw material that electronic balance, which weighs the copper source that mass ratio is 15% and chlorine stannous source, is added in beaker and uses deionized water
Magnetic agitation is completely dissolved to solution and clarifies.
（2）Weigh the polyvinylpyrrolidone of the oxalic acid and 2% solvent quality of the amount in 10 times of stannous sources mole（K=30）It is added
（1）In middle beaker, magnetic agitation is dissolved to solution secondary clearing again.
（3）Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method, and 200 DEG C of constant temperature keep the temperature 12h.
（4）After the completion of reaction, product is collected by centrifugation in washing three times respectively for deionized water and alcohol.
（5）It is prepared by heater-type gas sensor：Add absolute ethyl alcohol to be ground to uniform paste the product that experiment is collected into, uses
Fine, soft fur pen is coated in on gold electrode alumina ceramic tube.After ceramic tube welding encapsulation, the aging 5 on 4.5V agingtables
It, has been prepared gas sensor.Air-sensitive test is completed on WS-30A, and uses the hydrogen sulfide gas of 10% concentration in the process.
Embodiment 3：
（1）It is raw material that electronic balance, which weighs the copper source that mass ratio is 20% and chlorine stannous source, is added in beaker and uses deionized water
Magnetic agitation is completely dissolved to solution and clarifies.
（2）Weigh the polyvinylpyrrolidone of the oxalic acid and 2% solvent quality of the amount in 10 times of stannous sources mole（K=30）It is added
（1）In middle beaker, magnetic agitation is dissolved to solution secondary clearing again.
（3）Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method, and 200 DEG C of constant temperature keep the temperature 12h.
（4）After the completion of reaction, product is collected by centrifugation in washing three times respectively for deionized water and alcohol.
（5）It is prepared by heater-type gas sensor：Add absolute ethyl alcohol to be ground to uniform paste the product that experiment is collected into, uses
Fine, soft fur pen is coated in on gold electrode alumina ceramic tube.After ceramic tube welding encapsulation, the aging 5 on 4.5V agingtables
It, has been prepared gas sensor.Air-sensitive test is completed on WS-30A, and uses the hydrogen sulfide gas of 10% concentration in the process.
Table 1 is the copper and tin dioxide composite material prepared by embodiment 1-3, at 120 DEG C to 10ppm hydrogen sulfide gas
Response sensitivity.
Claims (4)
1. the preparation method of a kind of copper and the compound hydrogen sulfide gas sensitive of tin oxide, which is copper simple substance and tin oxide
Composite material, pattern is rounded bulbous, and size is within 300nm, for the application of the hydrogen sulfide gas detection of 10% concentration,
It is characterized in that, preparation method comprises the steps of：
（1）It is raw material that electronic balance, which weighs the copper source that mass ratio is 15% and chlorine stannous source, is added in beaker and uses deionized water magnetic force
Stirring is completely dissolved to solution and clarifies；
（2）Step is added in the polyvinylpyrrolidone that the K of the oxalic acid and 2% solvent quality that weigh the amount in 10 times of stannous sources mole is 30
Suddenly（1）In middle beaker, magnetic agitation is dissolved to solution secondary clearing again；
（3）Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method, and 200 DEG C of constant temperature keep the temperature 12h；
（4）After the completion of reaction, product is collected by centrifugation in washing three times respectively for deionized water and alcohol；
（5）It is prepared by heater-type gas sensor：Add absolute ethyl alcohol to be ground to uniform paste the product that experiment is collected into, uses fine, soft fur
Pen, which is coated in, to be carried on gold electrode alumina ceramic tube, after ceramic tube welding encapsulation, aging 5 days on 4.5V agingtables, and system
It is standby to have obtained gas sensor.
2. the preparation method of a kind of copper and the compound hydrogen sulfide gas sensitive of tin oxide, which is copper simple substance and tin oxide
Composite material, pattern is rounded bulbous, and size is within 300nm, for the application of the hydrogen sulfide gas detection of 10% concentration,
It is characterized in that, preparation method comprises the steps of：
（1）It is raw material that electronic balance, which weighs the copper source that mass ratio is 20% and chlorine stannous source, is added in beaker and uses deionized water magnetic force
Stirring is completely dissolved to solution and clarifies；
（2）The polyvinylpyrrolidone that the K of the oxalic acid and 2% solvent quality that weigh the amount in 10 times of stannous sources mole is 30 is added（1）
In middle beaker, magnetic agitation is dissolved to solution secondary clearing again；
（3）Reaction solution is put into hydro-thermal reaction baking oven, one step hydro thermal method, and 200 DEG C of constant temperature keep the temperature 12h；
（4）After the completion of reaction, product is collected by centrifugation in washing three times respectively for deionized water and alcohol；
（5）It is prepared by heater-type gas sensor：Add absolute ethyl alcohol to be ground to uniform paste the product that experiment is collected into, uses fine, soft fur
Pen is coated in on gold electrode alumina ceramic tube；After ceramic tube welding encapsulation, aging 5 days on 4.5V agingtables, system
It is standby to have obtained gas sensor.
3. the preparation method of a kind of copper according to claim 1 or claim 2 and the compound hydrogen sulfide gas sensitive of tin oxide, feature
It is, the unlimited duration of magnetic agitation, the clarification of final reaction solution.
4. the preparation method of a kind of copper according to claim 1 or claim 2 and the compound hydrogen sulfide gas sensitive of tin oxide, feature
It is, hydro-thermal reaction baking oven is hydrothermal reaction kettle, and the filling rate of hydrothermal reaction kettle is equal to or less than 60%.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105548263B (en) * | 2016-01-29 | 2018-05-01 | 武汉工程大学 | Hydrogen sulfide gas sensitive and its preparation and the preparation method of stink damp sensing device |
| CN106546702A (en) * | 2016-11-03 | 2017-03-29 | 武汉微纳传感技术有限公司 | A kind of volatile organic matter gas sensitive material and its manufacture method |
| CN107085027B (en) * | 2017-05-25 | 2019-01-18 | 福州大学 | A kind of composite nano materials and its preparation method and application of room temperature detection hydrogen sulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476110A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of hydrogen sulfide semiconductor sensor gas sensitive element |
| CN101140254A (en) * | 2007-10-16 | 2008-03-12 | 上海大学 | Method for enhancing air-sensitive performance of metal oxide semiconductor material |
| CN104502413A (en) * | 2014-12-18 | 2015-04-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material as well as preparation and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476110A (en) * | 2003-07-10 | 2004-02-18 | 上海大学 | Manufacturing method of hydrogen sulfide semiconductor sensor gas sensitive element |
| CN101140254A (en) * | 2007-10-16 | 2008-03-12 | 上海大学 | Method for enhancing air-sensitive performance of metal oxide semiconductor material |
| CN104502413A (en) * | 2014-12-18 | 2015-04-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material as well as preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| Cu掺杂对氧化锡纳米晶结构、形貌及其光学性能的影响;伦宁 等;《山东大学学报（工学版）》;20031231;第33卷(第6期);605-609 * |
| 一维Pt/SnO2纳米纤维的制备及NOx气敏性研究;徐爽 等;《无机材料学报》;20130630;第28卷(第6期);584-588 * |
| 球形SnO2微晶水热法制备与表征;李子荣 等;《安徽科技学院学报》;20101231;第24卷(第2期);48-51 * |
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