CN102680537A - Method for preparing high-selectivity stannic oxide/carbon nanometer tube gas sensor - Google Patents
Method for preparing high-selectivity stannic oxide/carbon nanometer tube gas sensor Download PDFInfo
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- CN102680537A CN102680537A CN2011100594345A CN201110059434A CN102680537A CN 102680537 A CN102680537 A CN 102680537A CN 2011100594345 A CN2011100594345 A CN 2011100594345A CN 201110059434 A CN201110059434 A CN 201110059434A CN 102680537 A CN102680537 A CN 102680537A
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Abstract
The invention provides a method for preparing a high-selectivity stannic oxide/carbon nanometer tube gas sensor. The method comprises the following steps of: adopting Al2O3 as a template, dipping the Al2O3 template in a stannic chloride solution with a certain concentration as the sizes and the structures of holes on the Al2O3 template are uniform, uniformly distributing the stannic chloride on the surface of the Al2O3 template, and oxidizing the stannic chloride to be a gas-sensing material stannic chloride through burning; then, limiting the growth of the gas-sensing material stannic chloride by using an acetylene gas pyrolysis method and utilizing the hole structure of the Al2O3 template, and making carbon attach finally; and obtaining a carbon nanometer tube/ stannic oxide composite material by removing the Al2O3 from a sodium hydroxide solution. The composite material is used for preparing a sensor, compared with the gas-sensing performance of the sensor in the market, the sensitivity and the selectivity of methane gas are greatly enhanced by the composite material. The method provided by the invention has the advantages of simple technology, convenience in operation and low cost, and has a wide industrial application prospect.
Description
Technical field
The present invention relates to the semiconductor sensing technical field, especially relate to the method for making of a kind of high selectivity tin ash/carbon nano-tube gas-sensitive sensors spare.
Background technology
In the use of combustion gas, safety is extremely important.I find that existing a lot of kitchen range and water heater have all attached Fuel Gas Leak Alarm.But a lot of rising still can take place every year in the rock gas deflagration accident having in Shanghai, and this type of explosion accident often all can cause the loss of property, even also can cause the injures and deaths of the person sometimes.
Owing in the environment in kitchen, the existence of oil smoke is often arranged, contains a lot of organic molecules in the oil smoke, hydrocarbons.These gases can be adsorbed on the gas surface, and variation equally can have a resistance.So sensor also can produce response to these gases.Because sensor can not be distinguished natural gas leaking and kitchen fume well, will produce and report by mistake and fail to report, cause potential safety hazard.
SnO
2As a kind of good N-type semiconductor material, have broad energy gap (Eg=3.6eV, T=300K).Because it has good anti-flammability, special photoelectric properties and gas-sensitive property, is widely used in technical fields such as gas sensor, humidity-sensitive material, liquid crystal display, lithium battery, catalyzer, photo-detector, semiconductor element, electrode material, protective finish and solar cell.
Because the gas sensing property mechanism of tin ash belongs to surperficial contact-type, concrete is: work as SnO
2With reducibility gas such as H
2, CO, CH
4, C
2H
5When OH etc. contact, can make SnO
2The charge carrier increase be that electron concentration increases, resistivity reduces, the resistance that finally reflects; As contact with oxygen voltinism gas such as O
2, NO
XDeng the time, material electronics concentration reduces, resistance increases.Utilize SnO
2Sensitivity that show is different to the variation of the resistivity of gas with various is different, again because the difference of sensitivity and with different gas contact the time, sensor then can embody its selection performance for certain gas.Because its surperficial control type, when contact with gas, the structure of specific surface area and material is in the effect of playing key aspect the raising of its performance and the improvement.
The present invention proposes and has prepared Performances of Novel Nano-Porous mitron/tin ash composite air-sensitive material, has prepared gas sensor.This method reaction conditions is gentle, and is simple to operate, can be mass-produced, and with short production cycle, have the wide industrial application prospect.
Summary of the invention
The method for making that the purpose of this invention is to provide a kind of high selectivity tin ash/carbon nano-tube gas-sensitive sensors spare.
This method may further comprise the steps:
A. at first take by weighing a certain amount of Al
2O
3Template, and it is at high temperature carried out pre-service in muffle furnace, it carries out activation.Meanwhile, take by weighing the SnCl of respective amount
49H
2O, and it is dissolved in the distilled water, and add an amount of hydrochloric acid to prevent SnCl
4Hydrolysis, on magnetic stirring apparatus, stir; Al
2O
3Template and SnCl
49H
2The mass ratio of O is 2: 3;
B. pre-service is good alumina formwork joins in the above-mentioned solution, and the processing that vacuumizes, to reach SnCl
4Be immersed in the effect in the duct of alumina formwork, and aluminum alloy pattern plate is taken out, carry out drying, SnCl
4Particle will to be evenly distributed in the duct of alumina formwork inner;
C. above-mentioned material is placed muffle furnace, under 600 ℃, carry out calcination processing, SnCl
4Be oxidized to gas sensitive SnO
2
D. the above-mentioned material that obtains is placed the chemical vapor deposition tubular furnace, fed acetylene gas 5 minutes earlier, expel with the gases such as air in will managing.Carry out then in the process of ventilation, heating, heating-up temperature is 800 ℃.Acetylene gas can get into the duct of alumina formwork in this process; And under the condition of anaerobic heat, decompose; The carbon that forms can form the CNT of tubular structure attached to the duct inside surface, and the tin ash that a last step obtains can be embedded on the inwall of CNT.
E. with in the sodium hydroxide solution of above-mentioned material as for 0.5mol/L, on magnetic stirring apparatus, stir 6h to reach the effect of removing alumina formwork fully;
F. above-mentioned solution filtration, oven dry can be obtained the carbon nano tube/tin dioxide compound substance;
G. the material with above-prepared adopts common thick film sensor technology of preparing to be prepared into high-selective gas transducer.
The principle and the characteristics of the inventive method are: in the inventive method, adopt Al
2O
3As template, because the size structure in hole is even on the template, be immersed in the certain density tin chloride solution, tin chloride will be distributed to the surface of aluminium oxide uniformly, through calcining tin chloride will be oxidized to gas sensitive tin oxide.Then, through the method for acetylene gas pyrolysis, utilize Al
2O
3The pore passage structure of template limits its growth, and carbon is adhered to.Just obtained the carbon nano tube/tin dioxide compound substance after aluminium oxide removed in sodium hydroxide solution.Become the sensor on sensor and the market to carry out the comparison of air-sensitive performance synthetic material preparation, gained material of the present invention strengthens the sensitivity and the selectivity of methane gas greatly.
The present invention makes things convenient for technology simple, and is easy to operate, and with low cost.Product of the present invention has air-sensitive effect preferably.
Description of drawings
Fig. 1 is the whole Electronic Speculum transmission effects synoptic diagram of the embodiment of the invention 1 gained carbon nano tube/tin dioxide compound substance.
The local Electronic Speculum transmission effects synoptic diagram of Fig. 2 embodiment of the invention 1 gained carbon nano tube/tin dioxide compound substance.
Fig. 3 processes the air-sensitive performance figure behind the sensor for the material that obtains among the embodiment 1.
Embodiment
For better elaboration the present invention, further describe below in conjunction with instantiation:
Embodiment 1
The method for making of a kind of high selectivity tin ash/carbon nano-tube gas-sensitive sensors spare, this method may further comprise the steps:
(1) at first on electronic balance, takes by weighing the Al of 4.0g
2O
3Template, and it is at high temperature carried out pre-service in muffle furnace removing the impurity substances of alumina surface, and is carried out activation with it.Meanwhile, take by weighing the SnCl of 6.0g
49H
2O, and it is dissolved in the distilled water of 100ml, and add an amount of hydrochloric acid to prevent SnCl
4Hydrolysis, on magnetic stirring apparatus, stir.
(2) pre-service is good alumina formwork joins in the above-mentioned solution, and the processing that vacuumizes, and then aluminum alloy pattern plate is taken out, and carries out drying, SnCl
4Particle will to be evenly distributed in the duct of alumina formwork inner.
(3) above-mentioned material is placed muffle furnace, under 600 ℃, carry out calcination processing, SnCl
4Be oxidized to gas sensitive SnO
2
(4) the above-mentioned material that obtains is placed the chemical vapor deposition tubular furnace, fed acetylene gas 5 minutes earlier, expel with the gases such as air in will managing.Carry out then in the process of ventilation, heating, heating-up temperature is 800 ℃, and the time is 1h.
The above-mentioned material that (5) will obtain places 5% onium hydroxide solution, on magnetic stirring apparatus, stirs 6h to reach the effect of removing alumina formwork fully.
(6) above-mentioned solution filtration, oven dry can be obtained final carbon nano tube/tin dioxide compound substance.
Embodiment 2
Step in the present embodiment and the foregoing description 1 are identical.Different is: do not have the dipping of the stannous chloride of second step in the present embodiment, finally make CNT.
Embodiment 3
Step in the present embodiment and the foregoing description 1 are identical.Different is: the SnCl in the first step among this embodiment
49H
2The addition of O changes 3.0g into, and finally makes the carbon nano tube/tin dioxide compound substance.
Embodiment 4
Step in the present embodiment and the foregoing description 1 are identical.Different is: the SnCl in the first step among this embodiment
49H
2The addition of O changes 9.0g into, finally makes the carbon nano tube/tin dioxide compound substance.
Step in the present embodiment and the foregoing description 1 are identical.Different is: in the heating process of the ventilation among this embodiment in the 4th step, heating-up temperature is 600 ℃, finally makes the carbon nano tube/tin dioxide compound substance.
Embodiment 6
Step in the present embodiment and the foregoing description 1 are identical.Different is: in the heating process of the ventilation of the 4th among this embodiment in the step, change 2h heat time heating time into, finally make the carbon nano tube/tin dioxide compound substance.
Above embodiment 2, embodiment 3, embodiment 4, and embodiment 5, and the product carbon nano tube/tin dioxide compound substance of embodiment 6 all has similar TEM figure with embodiment 1.
Products therefrom carbon nano tube/tin dioxide compound substance among Comparative Examples of the present invention and the embodiment is carried out tem analysis, and test its air-sensitive performance methane.
TEM instrument detecting to the carbon nano tube/tin dioxide compound substance:
Like Fig. 1, shown in Figure 2, be Electronic Speculum (TEM) the transmission effects synoptic diagram of gained carbon nano tube/tin dioxide compound substance among the embodiment 1.Adopt NEC's JEOL field emission high resolution scanning electron microscope (JSM-6700F) and the JEOL of NEC transmission electron microscope (JEOL 200CX) to observe the pattern of carbon nano tube/tin dioxide compound substance; Can know from Fig. 1; Embodiment 1 has synthesized the uniform CNT of structure; Can know by Fig. 2, stannic oxide particle all and be attached on the carbon pipe.
As shown in Figure 3; The sensitivity curve of the senser element of material preparation, dimethyl nitramine, benzopyrene, methylnaphthalene, methane, carbon monoxide when in the test concentration being respectively 50ppm, 100ppm, 150ppm, 200ppm, 250ppm have carried out the test of air-sensitive performance.Can see, very high to the sensitivity of methane, and to the principal ingredient of oil smoke such as dimethyl nitramine, benzopyrene, methylnaphthalene, be insensitive basically.
Although the present invention describes according to its preferred implementation, there are the change, displacement and the various substitute equivalents that fall in the scope of the invention.Here the example that provides only is illustrative, rather than limitation of the present invention.
For the sake of simplicity, this instructions has omitted the description to known technology.
Claims (2)
1. the method for making of high selectivity tin ash/carbon nano-tube gas-sensitive sensors spare is characterized in that the method includes the steps of:
A. at first take by weighing a certain amount of Al
2O
3Template, and it is at high temperature carried out pre-service in muffle furnace, it carries out activation.Meanwhile, take by weighing the SnCl of respective amount
49H
2O, and it is dissolved in the distilled water, and add an amount of hydrochloric acid to prevent SnCl
4Hydrolysis, on magnetic stirring apparatus, stir;
B. pre-service is good alumina formwork joins in the above-mentioned solution, and the processing that vacuumizes, to reach SnCl
4Be immersed in the effect in the duct of alumina formwork, and aluminum alloy pattern plate is taken out, carry out drying, SnCl
4Particle will to be evenly distributed in the duct of alumina formwork inner;
C. above-mentioned material is placed muffle furnace, under 600 ℃, carry out calcination processing, SnCl
4Be oxidized to gas sensitive SnO
2
D. the above-mentioned material that obtains is placed the chemical vapor deposition tubular furnace, fed acetylene gas 5 minutes earlier, expel with the gases such as air in will managing.Carry out then in the process of ventilation, heating; Heating-up temperature is 800 ℃; Acetylene gas can get into the duct of alumina formwork in this process, and under the condition of anaerobic heat, decomposes, and the carbon of formation can be attached to the duct inside surface; Form the CNT of tubular structure, and the tin ash that a last step obtains can be embedded on the inwall of CNT.
E. with in the sodium hydroxide solution of above-mentioned material as for 0.5mol/L, on magnetic stirring apparatus, stir 6h to reach the effect of removing alumina formwork fully;
F. above-mentioned solution filtration, oven dry can be obtained the carbon nano tube/tin dioxide compound substance;
G. the material with above-prepared adopts common thick film sensor preparation method, is prepared into gas sensor, is applied to methane gas and detects.
2. the method for making of a kind of selectivity tin ash as claimed in claim 1/carbon nano-tube gas-sensitive sensors spare is characterized in that: said Al
2O
3Template and SnCl
49H
2The mass ratio of O is 2: 3.
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|---|---|---|---|
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|---|---|---|---|
| CN2011100594345A CN102680537A (en) | 2011-03-11 | 2011-03-11 | Method for preparing high-selectivity stannic oxide/carbon nanometer tube gas sensor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136870A (en) * | 2015-09-22 | 2015-12-09 | 电子科技大学 | Hydrogen gas sensor and production method thereof |
| CN105489874A (en) * | 2014-09-17 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Stannic oxide nanoparticles with high electrical property and preparation method therefor |
| CN106299390A (en) * | 2015-06-24 | 2017-01-04 | 中国科学院金属研究所 | Nano-particle is embedded in nano composite material and the preparation method of CNT tube wall |
| CN108589260A (en) * | 2018-04-08 | 2018-09-28 | 上海理工大学 | A kind of preparation method for detecting the graded structure tin dioxide gas-sensitive material of formaldehyde gas |
| CN114890460A (en) * | 2022-05-17 | 2022-08-12 | 山东建筑大学 | Method for preparing perovskite nano material based on elliptic paraboloid-shaped aluminum oxide template |
-
2011
- 2011-03-11 CN CN2011100594345A patent/CN102680537A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489874A (en) * | 2014-09-17 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Stannic oxide nanoparticles with high electrical property and preparation method therefor |
| CN106299390A (en) * | 2015-06-24 | 2017-01-04 | 中国科学院金属研究所 | Nano-particle is embedded in nano composite material and the preparation method of CNT tube wall |
| CN106299390B (en) * | 2015-06-24 | 2019-01-18 | 中国科学院金属研究所 | Nano particle is embedded in the nanocomposite and preparation method of carbon nanotube tube wall |
| CN105136870A (en) * | 2015-09-22 | 2015-12-09 | 电子科技大学 | Hydrogen gas sensor and production method thereof |
| CN108589260A (en) * | 2018-04-08 | 2018-09-28 | 上海理工大学 | A kind of preparation method for detecting the graded structure tin dioxide gas-sensitive material of formaldehyde gas |
| CN108589260B (en) * | 2018-04-08 | 2021-07-13 | 上海理工大学 | Preparation method of tin dioxide gas-sensitive material with hierarchical structure for detecting formaldehyde gas |
| CN114890460A (en) * | 2022-05-17 | 2022-08-12 | 山东建筑大学 | Method for preparing perovskite nano material based on elliptic paraboloid-shaped aluminum oxide template |
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Application publication date: 20120919 |