CN101813654A - Method for preparing ethanol sensitive material with fine graded porous structure - Google Patents
Method for preparing ethanol sensitive material with fine graded porous structure Download PDFInfo
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- CN101813654A CN101813654A CN 201010165847 CN201010165847A CN101813654A CN 101813654 A CN101813654 A CN 101813654A CN 201010165847 CN201010165847 CN 201010165847 CN 201010165847 A CN201010165847 A CN 201010165847A CN 101813654 A CN101813654 A CN 101813654A
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- porous structure
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Abstract
The invention discloses a method for preparing an ethanol sensitive material with a fine graded porous structure in the technical field of sensitive materials. A natural butterfly wing adopted as a structural template is pretreated and then placed in tin salt impregnation liquid to perform impregnation, and then the natural butterfly wing is subjected to oxidation firing treatment to form a metal oxide material with a fine graded porous structure. The preparation method is simple and flexible and has low cost; and the prepared gas sensitive material with the fine graded porous structure is a good ethanol gas sensitive material, and can have high selection sensitivity on ethanol at a lower temperature.
Description
Technical field
What the present invention relates to is a kind of method of sensing material technical field, specifically is a kind of preparation method of fine graded porous structure ethanol sensitive material.
Background technology
Along with industrial expansion, inflammable, the explosion hazard gases of widespread use in production, transportation, use in case leak, will initiation fire even explosion accident, had a strong impact on people's the security of the lives and property.And because this class accident has sudden strong, characteristics such as the rescue difficulty is big, damaging range is wide, therefore in time monitoring the aerial content of these gases reliably seems particularly important.
In being used as the various types of materials of gas sensor, metal oxide semiconductor such as SnO
2, Fe
2O
3, ZnO etc. with cheap, volume is little, simple in structure, highly sensitive, response advantages such as resume speed is fast have occupied the bigger market share.But these metal oxide gas sensitives still are subject to higher working temperature and unfavorable selectivity in actual applications at present, for example, are about 300 ℃ in working temperature, SnO
2To ethanol, acetone, CO, H
2All show higher sensitivity etc. a series of gases, be difficult to specific gas such as ethanol are carried out selectivity identification.Present stage is existing to studies show that graded porous structure can improve the selectivity of gas sensitive, and reduces working temperature, is considered to improve the effective way of the air-sensitive performance of metal oxide semiconductor material.Therefore, the metal oxide of developing a kind of fine graded porous structure is used as gas sensitive, can monitor gases such as ethanol easy, sensitive, fast, accurately, economically and will have very big market application foreground.
Find by literature search, be used for the existing report of gas sensor that ethanol detects, as Chinese patent CN 1837803A " SnO
2The cluster nano-rod gas sensor ", prepared SnO in this patent
2The cluster nano-rod gas sensor has high sensitivity, selectivity and stability to the ethanol (500-1000ppm) of higher concentration.But its preparation process is loaded down with trivial details, the SnO of gained
2The scattered distribution of nano rod connects not closely, has limited its selectivity identification and stability thereof at low-concentration ethanol gas.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of fine graded porous structure ethanol sensitive material is provided, preparation technology's simple and flexible, with low cost, the gas sensitive of this fine graded porous structure of preparation can have high selection sensitivity to ethanol under lower temperature.
The present invention is achieved by the following technical solutions, and it is stay in place form that the present invention adopts natural butterfly's wing, is placed in the pink salt maceration extract through pre-service and floods, and handles the ethanol sensitive material that obtains fine graded porous structure through the oxidation calcination then.
Described butterfly is meant: special-shaped purple plague purpura butterfly, and available from She Shan botanical garden, Shanghai.
Described pre-service is meant: the rinsing in absolute ethyl alcohol of natural butterfly's wing is clean, and butterfly wing color becomes bottle green by purple.
Described pink salt maceration extract is meant: a kind of in stanniferous salpeter solution, stannous chloride ethanolic solution or the stannous sulfate ethanolic solution, wherein the stanniferous salpeter solution is meant that it is the HNO of 2M that the tin metal powder is added concentration
3It is faint yellow to be stirred to solution becomes in the solution, and the filtrate that obtains after leaving standstill filtration is the pink salt maceration extract; The concentration of stannous chloride ethanolic solution or stannous sulfate ethanolic solution is 1M.
Described dip treating is meant: natural butterfly's wing through pre-service surperficial ethanol not fully the volatilization before, when changing bluish violet into as yet, the surface color that promptly shows as the butterfly wing do not insert immediately in the pink salt maceration extract, flooded 6-24 hour, and took out then, put into 60 ℃ of dryings of drying box through alcohol wash.
Described oxidation calcination is handled and is meant: the butterfly wing after the dip treating is placed oxidation furnace, with 1-35 ℃/minute programming rate be warming up to 450-550 ℃ and be incubated 1-3 hour after naturally cool to room temperature, obtain white flakes shape product and be ethanol sensitive material with butterfly wing form fine hiberarchy.
The natural biologic material butterfly wing that the present invention will have a fine graded porous structure is applied to the preparation of gas sensitive, a kind of with low cost, simple environmental protection of technology and gas sensitive preparation method have efficiently been invented, prepared gas sensitive has the fine graded porous structure feature, can to ethanol outstanding selection susceptibility be arranged under lower temperature.The gas sensitive of the present invention preparation can be applied to that the traffic police checks that the driver drives when intoxicated, brewery, fermentation industry ethanol warning device etc., in field such as electric, industrial, civilian good prospects for application is arranged.This material will be guaranteed the safety and the stability of relevant chemical enterprise operation in the application in these fields, and people's lives safety is played guaranteeing role.
Description of drawings
Fig. 1 is the FESEM figure (a) of product in the embodiment of the invention 3 and the selection sensitivity map (b) of the relative gas with various of alcohol.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The tin metal powder adds the HNO of 2M
3It is faint yellow to be stirred to solution becomes in the solution, filters to obtain maceration extract.The rinsing in absolute ethyl alcohol of butterfly wing is clean, at absolute ethyl alcohol before the bone dry volatilization, when showing as butterfly wing color and being about to become bluish violet by bottle green, the pink salt maceration extract that is disposed above rapidly the butterfly wing of handling well being placed soaked 24 hours, take out the butterfly wing, after alcohol wash, put into drying box and carry out drying for 60 ℃, further put into oxidation furnace and carry out the calcination processing, be warming up to 550 ℃ with 2 ℃/minute programming rates, be incubated and naturally cool to room temperature after 1.5 hours, obtain white flakes shape product and be rutile phase tin ash (JCPD41-1445) with butterfly wing form fine graded porous structure.Its grain size is about 7.0nm, and specific surface area and voidage are respectively 51m
2g
-1And 0.14cm
3g
-1This oxide material is after grinding, with proper amount of deionized water and an amount of ethylene glycol furnishing pasty state, and evenly apply at the aluminium oxide ceramics tube-surface, through 500 ℃ of annealing 1 hour, make the gas sensor of graded porous structure, when working temperature is 140-200 ℃, show as selection sensitivity S alcohol gas
Ethanol/ S
i＞5 (i=acetone, methyl alcohol, NH
3, CO, H
2).
Embodiment 2
The tin metal powder adds the HNO of 2M
3It is faint yellow to be stirred to solution becomes in the solution, filters to obtain maceration extract.The rinsing in absolute ethyl alcohol of butterfly wing is clean, at absolute ethyl alcohol before the bone dry volatilization, when showing as butterfly wing color and being about to become bluish violet by bottle green, the pink salt maceration extract that is disposed above rapidly the butterfly wing of handling well being placed soaked 18 hours, take out the butterfly wing, after alcohol wash, put into drying box and carry out drying for 60 ℃, further put into oxidation furnace and carry out the calcination processing, be warming up to 550 ℃ with 2 ℃/minute programming rates, be incubated and naturally cool to room temperature after 1.5 hours, obtain white flakes shape product and be rutile phase tin ash (JCPD41-1445) with butterfly wing form fine graded porous structure.Its grain size is about 7.0nm, and specific surface area and voidage are respectively 50m
2g
-1And 0.15cm
3g
-1This oxide material is after grinding, with proper amount of deionized water and an amount of ethylene glycol furnishing pasty state, and evenly apply at the aluminium oxide ceramics tube-surface, through 500 ℃ of annealing 1 hour, make the gas sensor of graded porous structure, when working temperature is 140-200 ℃, show as selection sensitivity S alcohol gas
Ethanol/ S
i＞8 (i=acetone, methyl alcohol, NH
3, CO, H
2).
Embodiment 3
The tin metal powder adds the HNO of 2M
3It is faint yellow to be stirred to solution becomes in the solution, filters to obtain maceration extract.The rinsing in absolute ethyl alcohol of butterfly wing is clean, at absolute ethyl alcohol before the bone dry volatilization, when showing as butterfly wing color and being about to become bluish violet by bottle green, the pink salt maceration extract that is disposed above rapidly the butterfly wing of handling well being placed soaked 14 hours, take out the butterfly wing, after alcohol wash, put into drying box and carry out drying for 60 ℃, further put into oxidation furnace and carry out the calcination processing, be warming up to 550 ℃ with 2 ℃/minute programming rates, be incubated and naturally cool to room temperature after 1.5 hours, obtain white flakes shape product and be rutile phase tin ash (JCPD41-1445) with butterfly wing form fine graded porous structure.Its grain size is about 7.0nm, and specific surface area and voidage are respectively 56m
2g
-1And 0.16cm
3g
-1This oxide material is after grinding, with proper amount of deionized water and an amount of ethylene glycol furnishing pasty state, and evenly apply at the aluminium oxide ceramics tube-surface, through 500 ℃ of annealing 1 hour, make the gas sensor of graded porous structure, when working temperature is 140-200 ℃, show as selection sensitivity S alcohol gas
Ethanol/ S
i＞10 (i=acetone, methyl alcohol, NH
3, CO, H
2).
At the air-sensitive property research of porous structure stannic oxide nano material, existing both at home and abroad many reports are as " The selectivedetection of C
2H
5OH using SnO
2-ZnO thin film gas sensors prepared by combinatorial solutiondeposition " (Sensors and actuators B 123 (2007) is 318-324) with " Enhanced performance of SnO
2Nanowires ethanol sensor by functionalizing with La
2O
3" (Sensors and actuators B 133 (2008), 228-234), this class material shows the selection sensitivity S to alcohol gas usually under 300-400 ℃ working temperature
Ethanol/ S
AcetoneBe about 2, and the prepared porous hierarchical structure stannic oxide nano material of the foregoing description under lower temperature (140-200 ℃) to the selection sensitivity S of alcohol gas
Ethanol/ S
Acetone＞5, obviously show good sensing capabilities to alcohol gas.
Claims (8)
1. the preparation method of the ethanol sensitive material of a fine graded porous structure is characterized in that, adopting natural butterfly's wing is stay in place form, is placed in the pink salt maceration extract through pre-service and floods, and handles obtaining ethanol sensitive material then through the oxidation calcination.
2. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 1 is characterized in that, described butterfly is meant special-shaped purple plague purpura butterfly.
3. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 1 is characterized in that, described pre-service is meant: the rinsing in absolute ethyl alcohol of natural butterfly's wing is clean, and butterfly wing color becomes bottle green by purple.
4. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 1 is characterized in that, described pink salt maceration extract is meant: a kind of in stanniferous salpeter solution, stannous chloride ethanolic solution or the stannous sulfate ethanolic solution.
5. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 4 is characterized in that, described stanniferous salpeter solution is meant: it is the HNO of 2M that the tin metal powder is added concentration
3It is faint yellow to be stirred to solution becomes in the solution, and the filtrate that obtains after leaving standstill filtration is the pink salt maceration extract.
6. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 4 is characterized in that, the concentration of described stannous chloride ethanolic solution or stannous sulfate ethanolic solution is 1M.
7. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 1, it is characterized in that, described dip treating is meant: the surperficial ethanol at pretreated natural butterfly's wing does not place the pink salt maceration extract before the bone dry volatilization immediately, be that the surface color of natural butterfly's wing is not when changing bluish violet into as yet, place tin-salt solution rapidly, dip treating 6-24 hour, take out then through alcohol wash, put into 60 ℃ of dryings of drying box.
8. the preparation method of the ethanol sensitive material of fine graded porous structure according to claim 1, it is characterized in that, described oxidation calcination is handled and is meant: the natural butterfly's wing after will flooding places oxidation furnace, with 1-35 ℃/minute programming rate be warming up to 450-550 ℃ and be incubated 1-3 hour after naturally cool to room temperature, obtain the ethanol sensitive material that white flakes shape product is fine graded porous structure.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389980A (en) * | 2011-11-28 | 2012-03-28 | 上海交通大学 | Carbon-layer-coated nano iron having butterfly wing microscopic structure and preparation method thereof |
| CN102717613A (en) * | 2012-03-31 | 2012-10-10 | 上海交通大学 | Method for preparing material with butterfly wing microstructure, stamp and embossing device |
| CN102815743A (en) * | 2012-08-17 | 2012-12-12 | 上海交通大学 | Gas sensitive material with single porous micron tube structure, preparation method and application thereof |
| CN103011900A (en) * | 2012-12-03 | 2013-04-03 | 上海交通大学 | Method for preparing fine air-sensitive sensing material of porous structure |
| CN104458815A (en) * | 2014-12-11 | 2015-03-25 | 郑州大学 | High-molecular gas sensitive material as well as preparation method and application thereof |
| CN110907503A (en) * | 2019-10-28 | 2020-03-24 | 深圳大学 | Manufacturing method of hierarchical porous structure metal oxide and metal oxide semiconductor gas sensor |
| CN116858922A (en) * | 2023-09-01 | 2023-10-10 | 天津理工大学 | High-performance gas sensing material for analyzing exhaled gas of human body and sensor |
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| CN101266225A (en) * | 2008-04-28 | 2008-09-17 | 吉林大学 | Electric spinning method for preparing high performance ceramic base nanometer fibre gas-sensitive sensor |
| CN101664675A (en) * | 2009-09-04 | 2010-03-10 | 上海交通大学 | Preparation method of photocatalysis materials of biomorphic fine hiberarchy |
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2010
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389980A (en) * | 2011-11-28 | 2012-03-28 | 上海交通大学 | Carbon-layer-coated nano iron having butterfly wing microscopic structure and preparation method thereof |
| CN102717613A (en) * | 2012-03-31 | 2012-10-10 | 上海交通大学 | Method for preparing material with butterfly wing microstructure, stamp and embossing device |
| CN102717613B (en) * | 2012-03-31 | 2016-06-01 | 上海交通大学 | There is the preparation method of material of butterfly wing microstructure, seal and Embosser |
| CN102815743A (en) * | 2012-08-17 | 2012-12-12 | 上海交通大学 | Gas sensitive material with single porous micron tube structure, preparation method and application thereof |
| CN102815743B (en) * | 2012-08-17 | 2014-08-27 | 上海交通大学 | Gas sensitive material with single porous micron tube structure, preparation method and application thereof |
| CN103011900A (en) * | 2012-12-03 | 2013-04-03 | 上海交通大学 | Method for preparing fine air-sensitive sensing material of porous structure |
| CN104458815A (en) * | 2014-12-11 | 2015-03-25 | 郑州大学 | High-molecular gas sensitive material as well as preparation method and application thereof |
| CN110907503A (en) * | 2019-10-28 | 2020-03-24 | 深圳大学 | Manufacturing method of hierarchical porous structure metal oxide and metal oxide semiconductor gas sensor |
| CN116858922A (en) * | 2023-09-01 | 2023-10-10 | 天津理工大学 | High-performance gas sensing material for analyzing exhaled gas of human body and sensor |
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Application publication date: 20100825 |