CN100592082C - Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device - Google Patents
Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device Download PDFInfo
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- CN100592082C CN100592082C CN200710053341A CN200710053341A CN100592082C CN 100592082 C CN100592082 C CN 100592082C CN 200710053341 A CN200710053341 A CN 200710053341A CN 200710053341 A CN200710053341 A CN 200710053341A CN 100592082 C CN100592082 C CN 100592082C
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Abstract
The invention relates to a formaldehyde gas sensitive material, the preparation method thereof and a manufacture method of a formaldehyde gas sensitive component. The component of the formaldehyde gassensitive material takes an SnO<SUB>2</SUB>-TiO<SUB>2</SUB> binary nanometer composite material as a substrate, the mol ratio of the Ti/Sn is 0.2 to 0.5, the fractional ratio of the quality adulterated is 2 percent to 5 percent Cd<SUP>2</SUP>, the formaldehyde gas sensitive material is adjusted to be pasty after being ground with an appropriate amount absolute ethyl alcohol and 0.2 to 1 portion polyethylene glycol, and is painted on the surface of an electrode pipe evenly, and a formaldehyde gas sensitive electrode pipe is produced through 400 degree annealing processing for two to four hours; finally a formaldehyde gas sensitive component is made through the welding, the electrical ageing and the sealing to the gas sensitive electrode pipe according to the heater type structure traditional process. The gas sensitive sensor made through the invention has low operating temperature, has high sensitivity to the formaldehyde gas, has good antiinterference performance to other indoor pollutant gases, such as benzene, toluene, xylene and ammonia, etc, the response time and the recovery time are short, and the gas sensitive sensor is used for the detection to the indoor decorating formaldehyde gas pollution.
Description
Technical field
The invention belongs to Metal Oxide Semiconductor Gas Sensing Element Technology field, be specifically related to the method for making of a kind of formaldehyde gas sensitive material and preparation method thereof and formaldehyde gas sensitive device.
Background technology
Formaldehyde is a kind of protoplasm poisonous substance that destroys biological cell protein, can people's skin, respiratory tract and internal organ be caused damage, and anesthesia people's nervous centralis causes pulmonary edema, hepatic coma, kidney failure etc.Formaldehyde pollution problem at present concentrates in room, the ornament materials.Scale board in indoor decoration material and the furniture, fiberboard, etc. contain in the artificial board in a large number based on the Lauxites of formaldehyde, all contain formaldehyde in all kinds of paint, the coating.Formaldehyde pollution problem serious threat health should cause showing great attention to of people, and content of formaldehyde has become an important safety index of current indoor pollution monitoring.
The research of gas sensor both at home and abroad now is most with metal-oxide semiconductor (MOS) SnO with production
2, ZnO, Fe
2O
3Be the main matrix material, 95% is the gas sensor of traditional heater-type structure in the home market.And, be in exploration, conceptual phase at home for the formaldehyde gas sensor, do not form commercialization as yet.Domestic detection for indoor formaldehyde gas is the method to test after the sampling still, and the release of formaldehyde gas is a process gradually, and therefore studying a kind of citizen formaldehyde gas sensor that can independently finish in the own home, easy, sensitive, quick, directly perceived, accurate, economic will have very big market outlook.
The first-selected semiconductor gas sensor of the optimal method of the detection of PARA FORMALDEHYDE PRILLS(91,95) dusty gas because it have reaction fast, highly sensitive, need not sample, on-the-spotly detect, advantage such as easy to use.Wherein desirable gas sensor depends on the performance of gas sensitive, and the exploitation of gas sensitive is the most key part in the gas sensor research field.
Summary of the invention
The object of the present invention is to provide formaldehyde gas sensitive material of a kind of economy, Validity Test formaldehyde gas and preparation method thereof.
Another object of the present invention provides a kind of method of making the formaldehyde gas sensitive device of formaldehyde gas sensitive material, the formaldehyde gas sensitive material of preparation of the present invention is made gas sensing electrode, and what adopt is that the preparation method of traditional sintering heater-type gas sensor makes the formaldehyde gas sensitive device again.
Technical scheme of the present invention is as follows:
The formaldehyde gas sensitive material component is with SnO
2-TiO
2The bielement nano composite powder is a matrix, and wherein the Ti/Sn mol ratio is 0.2-0.5, mixes massfraction than being the Cd of 2%-5%
2+
Above-mentioned SnO
2-TiO
2The bielement nano composite powder is a nanometer fine powder, mainly with Detitanium-ore-type TiO
2With tetragonal structure SnO
2Xiang Weizhu, particle diameter is at 20-100nm.
SnO
2-TiO
2The bielement nano composite powder is to be made by sol-gel process, and by volume part is got each raw material, gets 10 parts of Ti (OC
4H
9)
4Under stirring condition, dropwise be added in 26 parts of absolute ethyl alcohols, continue again to stir 30min, obtain shallow yellow transparent solution A; By the mol ratio of calculating Sn and Ti is that 0.2-0.5 gets SnCl
45H
2O joins in the solution A, stirs and makes the solution homogeneous transparent, obtains solution B; With 20 parts of absolute ethyl alcohols, 2 parts of concentration is to obtain colourless transparent solution C after 1mol/L HCl aqueous solution and 2-5 part distilled water mix; Solution C under stirring condition, dropwise is added in the solution B, obtains light yellow transparent solution, continue to stir 2h, sealing and standing obtains the ecru gel particle after the vacuum drying then; After xerogel ground refinement,, promptly obtain SnO at 450 ℃ of calcining 2h down
2-TiO
2The bielement nano composite powder is by changing SnCl
45H
2The amount of O obtains the SnO of the ratio of mol ratio Sn/Ti=0.2-0.5
2-TiO
2The bielement nano composite powder; The massfraction ratio is 2%-5%CdCl
2With SnO
2-TiO
2Bielement nano composite powder mixed grinding makes Cd
2+Be doped in the nano composite powder, with an amount of absolute ethyl alcohol and 0.2-1 part polyglycol furnishing pasty state, evenly be coated in the electrode tube surface again,, make formaldehyde gas sensing electrode pipe through 400 ℃ of annealing in process 2-4 hours.
The making step of formaldehyde gas sensitive device of the present invention is as follows:
1.SnO
2-TiO
2The preparation of binary composite nanometre powder:
By volume part is got each raw material, gets 10 parts of Ti (OC
4H
9)
4Under stirring condition, dropwise be added in 26 parts of absolute ethyl alcohols, continue again to stir 30min, obtain shallow yellow transparent solution A; By calculating mol ratio Sn/Ti is that 0.2-0.5 gets SnCl
45H
2O joins in the solution A, stirs and makes the solution homogeneous transparent, obtains B liquid; With 20 parts of absolute ethyl alcohols, 2 parts of concentration is to obtain colourless transparent solution C after 1mol/L HCl aqueous solution and 2-5 part distilled water mix; Solution C under stirring condition, dropwise is added in the solution B, obtains light yellow transparent solution, continue to stir 2h, sealing and standing obtains the ecru gel particle after the vacuum drying then; After xerogel ground refinement,, promptly obtain SnO at 450 ℃ of calcining 2h down
2-TiO
2The bielement nano composite powder is by changing SnCl
45H
2The amount of O obtains the SnO of the ratio of mol ratio Sn/Ti=0.2-0.5
2-TiO
2The bielement nano composite powder;
2. with the SnO of step 1 gained
2-TiO
2The bielement nano composite powder is 2%-5%CdCl with the massfraction ratio
2Mixed grinding makes Cd
2+Be doped in the nano composite powder, to improve the sensitivity and the selectivity of PARA FORMALDEHYDE PRILLS(91,95) gas, grind the back with an amount of absolute ethyl alcohol and 0.2-1 part polyglycol furnishing pasty state, evenly be coated in the electrode tube surface, through 400 ℃ of annealing in process 2-4 hours, make the core of formaldehyde gas sensitive device: formaldehyde gas sensing electrode pipe;
3, at last by heater-type structure traditional handicraft to the gas sensing electrode pipe weld, electricity wears out, encapsulate, make the formaldehyde gas sensitive device.
The characteristics of formaldehyde gas sensitive device compared with prior art of the present invention are as follows:
The present invention proposes a kind of new formaldehyde gas sensitive material, this material possesses the quantum effect of nano material, the self-catalysis activity, characteristics such as surface effect are simultaneously as a kind of gas sensitive newly developed, PARA FORMALDEHYDE PRILLS(91,95) gas sensitivity height, the resolution height selects performance good, the interference that can effectively differentiate interior decoration dusty gas such as gas PARA FORMALDEHYDE PRILLS(91,95) gas sensors such as benzene,toluene,xylene, ammonia, response time is short, working temperature is low, meets the requirement of the indoor formaldehyde gas sensor device of practical standard.
Formaldehyde gas sensitive device the key technical indexes of the present invention is as follows:
1, device sensing range: gas concentration 20ppm-1000ppm;
2, device working temperature: 260 ℃-300 ℃;
3, detection sensitivity: 12-60, concentration of formaldehyde 20ppm-1000ppm
4, Immunity Performance: to interference gas benzene,toluene,xylene, ammonia sensitivity≤5;
5, the device reaction time: less than 15s;
6, device release time: less than 32s.
Embodiment
Below the invention will be further described with example, but be not limited thereto.
Embodiment 1
Formaldehyde gas sensitive device making step:
1.SnO
2-TiO
2The preparation of bielement nano composite powder
Get 10ml Ti (OC
4H
9)
4Under stirring condition, dropwise be added in the 26ml absolute ethyl alcohol, continue again to stir 30min, obtain shallow yellow transparent solution A; By the mol ratio of calculating Sn and Ti is 0.3 to get SnCl
45H
2O joins in the solution A, stirs and makes the solution homogeneous transparent, obtains B liquid; With 20ml absolute ethyl alcohol, 2ml concentration is to obtain colourless transparent solution C after 1mol/L HCl aqueous solution and 2ml distilled water mix; Solution C under stirring condition, is added drop-wise in the solution B liquid, can obtains light yellow transparent solution and continue to stir 2h, sealing and standing obtains the yellow-white gel particle after the vacuum drying then; After xerogel ground refinement,, promptly obtain SnO at 450 ℃ of calcining 2h down
2-TiO
2The bielement nano composite powder;
With massfraction than the CdCl that is 2%
2SnO with step 1 gained
2-TiO
2Bielement nano composite powder mixed grinding makes Cd
2+Be doped in the nano composite powder, to improve the sensitivity and the selectivity of PARA FORMALDEHYDE PRILLS(91,95) gas, grind the back with an amount of absolute ethyl alcohol and 0.5ml polyglycol furnishing pasty state, evenly be coated in the electrode tube surface, through 400 ℃ of annealing in process 3 hours, make formaldehyde gas sensing electrode pipe;
3, at last by heater-type structure traditional handicraft PARA FORMALDEHYDE PRILLS(91,95) gas sensing electrode pipe weld, electricity is aging, encapsulation, makes the formaldehyde gas sensitive device.This device is specifically designed to the detection of interior decoration dusty gas formaldehyde, has fine vulnerability to jamming for other interior decoration dusty gass such as gases such as benzene,toluene,xylene, ammonia.
Implement mol ratio that formaldehyde gas sensitive device making step in 2 removes Sn and Ti and be 0.2 and get SnCl
45H
2The amount of O and SnO
2-TiO
2The bielement nano composite powder is pressed massfraction than 3% doping CdCl
2Outward, all the other are identical with example 1.
Implement mol ratio that formaldehyde gas sensitive device making step in 3 removes Sn and Ti and be 0.5 and get SnCl
45H
2The amount of O and SnO
2-TiO
2The bielement nano composite powder is pressed massfraction than 5% doping CdCl
2Outward, all the other are identical with example 1.
Claims (3)
1, formaldehyde gas sensitive material, material component is with SnO
2-TiO
2The bielement nano composite powder is a matrix, and wherein the Ti/Sn mol ratio is 0.2-0.5, mixes massfraction than being the Cd of 2%-5%
2+, described SnO
2-TiO
2TiO in the bielement nano composite powder
2Be Detitanium-ore-type TiO
2Phase, SnO
2Be tetragonal structure SnO
2Phase, particle diameter is at 20-100nm.
2, the preparation method of formaldehyde gas sensitive material carries out: (1), SnO according to the following steps
2-TiO
2The preparation of bielement nano composite powder: by volume part is got each raw material, gets 10 parts of Ti (OC
4H
9)
4Under stirring condition, dropwise be added in 26 parts of absolute ethyl alcohols, continue again to stir 30min, obtain shallow yellow transparent solution A; By calculating mol ratio Sn/Ti is that 0.2-0.5 gets SnCl
45H
2O joins in the solution A, stirs and makes the solution homogeneous transparent, obtains solution B; With 20 parts of absolute ethyl alcohols, 2 parts of concentration is to obtain colourless transparent solution C after 1mol/L HCl aqueous solution and 2-5 part distilled water mix; Solution C under stirring condition, is added drop-wise in the solution B, obtains light yellow transparent solution, continue to stir 2h, sealing and standing obtains the ecru gel particle after the vacuum drying then; After xerogel ground refinement,, obtain SnO at 450 ℃ of calcining 2h down
2-TiO
2The bielement nano composite powder; (2), with SnO
2-TiO
2The bielement nano composite powder by massfraction than the 2%-5% CdCl that mixes
2
3, the method for making of formaldehyde gas sensitive device is carried out: (1), SnO according to the following steps
2-TiO
2The preparation of binary composite nanometre powder: by volume part is got each raw material, gets 10 parts of Ti (OC
4H
9)
4Under stirring condition, dropwise be added in 26 parts of absolute ethyl alcohols, continue again to stir 30min, obtain shallow yellow transparent solution A; By calculating mol ratio Sn/Ti is that 0.2-0.5 gets SnCl
45H
2O joins in the solution A, stirs and makes the solution homogeneous transparent, obtains solution B; With 20 parts of absolute ethyl alcohols, 2 parts of concentration is to obtain colourless transparent solution C after 1mol/L HCl aqueous solution and 2-5 part distilled water mix; Solution C under stirring condition, is added drop-wise in the solution B, obtains light yellow transparent solution, continue to stir 2h, sealing and standing obtains the ecru gel particle after the vacuum drying then; After xerogel ground refinement,, promptly obtain SnO at 450 ℃ of calcining 2h down
2-TiO
2The bielement nano composite powder; (2) with the SnO of step (1) gained
2-TiO
2The bielement nano composite powder by massfraction than the 2%-5% CdCl that mixes
2, grind the back with an amount of absolute ethyl alcohol and 0.2-1 part polyglycol furnishing pasty state, evenly be coated in the electrode tube surface, through 400 ℃ of annealing in process 2-4 hours, make formaldehyde gas sensing electrode pipe; (3), at last by heater-type structure traditional handicraft to the gas sensing electrode pipe weld, electricity wears out, encapsulate, make the formaldehyde gas sensitive device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710053341A CN100592082C (en) | 2007-09-24 | 2007-09-24 | Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device |
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|---|---|---|---|
| CN200710053341A CN100592082C (en) | 2007-09-24 | 2007-09-24 | Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device |
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|---|---|
| CN101144789A CN101144789A (en) | 2008-03-19 |
| CN100592082C true CN100592082C (en) | 2010-02-24 |
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Families Citing this family (15)
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| CN101493430B (en) * | 2009-02-17 | 2012-05-30 | 武汉工程大学 | Hydrogen sulfide gas sensitive, preparation, and method for making hydrogen sulfide gas sensitive device |
| ES2359204B1 (en) * | 2009-11-09 | 2012-03-26 | Universitat Rovira I Virgili | DEVICE FOR THE SELECTIVE DETECTION OF GAS BENZENE, PROCEDURE FOR OBTAINING AND DETECTION OF GAS WITH THE SAME. |
| CN102680540B (en) * | 2012-06-07 | 2014-06-18 | 惠州市富济电子材料有限公司 | Formaldehyde gas-sensing material, corresponding formaldehyde gas-sensing element and preparation method of element |
| US9285349B2 (en) | 2012-11-07 | 2016-03-15 | Empire Technology Development Llc | Analyte detectors and methods for their preparation and use |
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
| CN104267068A (en) * | 2014-08-26 | 2015-01-07 | 吉林大学 | Acetone gas sensor based on alpha-Fe2O3/SnO2 composite nano fibers and preparation method thereof |
| CN104807860B (en) * | 2014-12-23 | 2017-09-01 | 郑州轻工业学院 | A kind of flower-like nanometer WO3/ graphenes composite air-sensitive material and its preparation method and application |
| CN105092655A (en) * | 2015-04-15 | 2015-11-25 | 天津科技大学 | Novel palladium porous silicon sensor for rapid detection of formaldehyde and preparation method thereof |
| CN105717168B (en) * | 2016-02-25 | 2018-03-27 | 济南大学 | A kind of preparation method and application of the these hydrogen sulfide gas sensor based on titanium dioxide nanoplate carried noble metal |
| CN106442644B (en) * | 2016-09-26 | 2019-01-15 | 吉林大学 | One kind being based on Ce5Sn3/Sn3O4The formaldehyde gas sensor and preparation method thereof of three-dimensional graded structure |
| CN107884455A (en) * | 2017-12-12 | 2018-04-06 | 朱明君 | A kind of refrigerator with formaldehyde examination device |
| CN108828010B (en) * | 2018-08-22 | 2021-03-02 | 云南大学 | Sensitive material for detecting formaldehyde gas, preparation method and application |
| CN110455977B (en) * | 2019-06-30 | 2021-06-08 | 北京联合大学 | Low-temperature catalytic luminescence sensitive material of formaldehyde and ammonia |
| CN110455900B (en) * | 2019-07-31 | 2022-05-24 | 广州大学华软软件学院 | Formaldehyde-sensitive composite material, gas-sensitive sensor and preparation method of formaldehyde-sensitive composite material |
| CN113670991B (en) * | 2021-09-08 | 2024-01-30 | 大连理工大学 | Hematite-based monocrystal room temperature gas-sensitive material exposing high-energy crystal face, and preparation method and application thereof |
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