CN103364453B - Tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method - Google Patents
Tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method Download PDFInfo
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- CN103364453B CN103364453B CN201310264387.7A CN201310264387A CN103364453B CN 103364453 B CN103364453 B CN 103364453B CN 201310264387 A CN201310264387 A CN 201310264387A CN 103364453 B CN103364453 B CN 103364453B
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Abstract
The invention discloses a kind of tin oxide-zinc oxide compound hollow microballoon gas sensor and preparation method thereof, tin oxide-zinc oxide compound hollow microballoon utilizes template synthesis, gas-sensitive sensor device adopts heater-type device architecture, taking alumina ceramic tube as carrier, there is heater strip earthenware inside, outer surface is with gold electrode, and two ends are by platinum wire extraction electrode. Scribble tin oxide-zinc oxide compound hollow microballoon gas sensitive in earthenware outside, after welding, encapsulation, obtain gas-sensitive sensor device. The invention has the advantages that: utilize the metal oxide microballoon that specific area is large to do gas sensitive, can greatly increase the active room of material surface; Improve responsiveness and the response time of gas sensor; The gas-sensitive sensor device that the present invention adopts is made simple, stable performance, highly sensitive, under operating temperature, ethanol is had to very high sensitivity, can be used for the detection of ethanol.
Description
Technical field
The present invention relates to a kind of gas-sensitive sensor device and preparation method thereof, particularly relate to a kind of tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method.
Background technology
The advantages such as metal oxide semiconductor Nano-meter Materials as Gas Sensors is highly sensitive owing to having, response is fast, volume is little, preparation method is simple, low price become gas-sensitive sensor device optimal material. The gas sensitive of development of new and novel gas-sensitive sensor device become one of main direction of domestic and international semiconductor gas sensor development at present.
ZnO microsphere is owing to having adjustable pore passage structure, high-specific surface area and stronger ion-exchange performance, be conducive to reactant reacts in active sites in catalytic process, detection aspect to gases such as ethanol, acetone, formaldehyde has shown greatly application prospect, and therefore ZnO nano-structure material is widely used in the sensitive material of gas sensor; SnO2Owing to ethanol being there is to good responsiveness, also become the only selection of gas sensor material. But independent zinc oxide or stannic oxide materials are poor to gas-selectively, can fully utilize the advantage of bi-material by preparing tin oxide-zinc oxide composite, realize the preparation of the gas sensor highly sensitive, the response time is short. Common report has ZnO/SnO at present2Nuclear shell structure nano line, SnO2The preparation of-ZnO composite powder and the application in gas-sensitive sensor device, the present invention proposes to utilize template synthesis SnO2-ZnO complex microsphere, the micro-sphere structure of rule has larger specific area and surface-active room, for market provides a kind of gas sensor material and device of high-quality.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method.
A preparation method for tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device, is characterized in that, comprises the steps:
(1) organic template is dissolved in organic solvent, after dissolving completely, adds the diethanol amine of zinc precursor body and 0.5 milliliter to 2.8 milliliters, or triethanolamine; Then at room temperature at least stir and within 3 hours, obtain zinc oxide precursor liquid solution;
(2) take tin presoma by tin presoma and zinc precursor body mol ratio 1:10～1:1, be placed in zinc precursor liquid solution, stir 2～4 hours, obtain tin-zinc compound precursor liquid solution;
(3) precursor solution is placed in to reactor, in 80～200 DEG C of reactions 12 hours to 24 hours;
(4) question response still temperature is down to room temperature, and milk-white coloured suspension is washed respectively 3～5 times with alcohol and water, obtains tin oxide-zinc oxide compound hollow microballoon, microballoon is placed in to alcohol or water is stand-by;
(5) for alumina ceramic tube, deionized water, acetone, chloroform clean up, dry for standby;
(6) suspension of tin oxide-zinc oxide compound hollow microballoon is evenly spread upon on alumina ceramic tube, earthenware is encapsulated;
(7) at 100～300 DEG C electricity aging 3～15 days, make tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device.
Organic template described in step (1) is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (P123), or di-block copolymer polystyrene-poly oxygen ethene or softex kw.
Organic solvent described in step (1) is a kind of or its combination in absolute ethyl alcohol, n-butanol, oxolane.
Zinc precursor body described in step (1) is the one in two water zinc acetates, zinc chloride, zinc nitrate hexahydrate, Zinc vitriol.
Tin presoma described in step (2) is stannic chloride, or stannous chloride.
The weight ratio of zinc precursor body, organic template and the organic solvent described in step (2) is 0.05～0.6:0.03～0.8:2～7.
The described washing methods of step (4) is centrifugal under 5000 ~ 15000 revs/min of rotating speeds or suction filtration method all can;
The described aging atmosphere of step (7) is air.
A kind of tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device, is characterized in that, prepares according to said method.
The invention has the advantages that: utilize the metal oxide microballoon that specific area is large to do gas sensitive, can greatly increase the active room of material surface; By preparing tin oxide-zinc oxide compound hollow microballoon, can make full use of the advantage of bi-material, improve responsiveness and the response time of gas sensor; Device architecture is taked heater-type structure, and surperficial gas sensitive is applied by pasty state zinc oxide compound hollow microballoon, can prepare uniform gas sensitive film; The gas-sensitive sensor device that the present invention adopts is made simple, stable performance, highly sensitive, under operating temperature, ethanol is had to very high sensitivity, can be used for the detection of ethanol.
Method of the present invention is to utilize hydro-thermal method to synthesize SnO2-ZnO compound hollow microballoon, regulates its specific area by this table of microballoon size, and then regulates and controls its surface-active room, makes it have higher responsiveness; Variation by Sn and Zn ratio improves gas-selectively, and device is prepared aspect, and gas sensitive is coated in to earthenware surface, and preparation technology is simple, reproducible. The method preparation technology is simple, has improved response efficiency by improving material specific area and surface-active room, has reduced response temperature, makes the application of nano material aspect gas sensor simpler.
Brief description of the drawings
Fig. 1 is the SEM figure of ZnO of the present invention and the SnO2 mol ratio microballoon that is 4:1, and as seen from the figure, microsphere diameter is between 2.5 ~ 3 microns.
Fig. 2 is the high power SEM figure of tin oxide-zinc oxide compound hollow microballoon of the present invention.
Fig. 3 is the energy spectrogram of tin oxide-zinc oxide compound hollow microballoon of the present invention, and EDS power spectrum has confirmed that microballoon is tin oxide, zinc oxide composite construction.
Fig. 4 is the air-sensitive response curve of the absolute ethyl alcohol of tin oxide-zinc oxide compound hollow microballoon of the present invention to variable concentrations, electrical response rate is up to 9, the variable concentrations response time, result showed all in 10s, and tin oxide-zinc oxide compound hollow microballoon shows good ethanol response.
Detailed description of the invention
Embodiment 1: take the block polymer P123 of 2g, be dissolved in the absolute ethyl alcohol of 25ml; Add the zinc acetate of 0.43g and the diethanol amine of 0.8ml, under room temperature, stir and within 3 hours, obtain zinc precursor liquid solution; The stannous chloride that takes 0.12g is placed in zinc precursor liquid solution, stirs 1 hour; Tin-zinc precursor solution is placed in to reactor, in 180 DEG C of reactions 24 hours; Use respectively alcohol and water centrifuge washing 3 times, obtain tin oxide-zinc oxide compound hollow microballoon; Microballoon is dissolved in and in absolute ethyl alcohol, obtains pastel; For alumina ceramic tube, deionized water, acetone, chloroform clean up, and dry, and tin oxide-zinc oxide compound hollow microballoon pastel is evenly coated in to earthenware surface, and welding electrode, encapsulation, obtain gas sensor. Microsphere diameter is between 2.5～3 microns, and the electrical response rate of the ethanol that tin oxide-zinc oxide compound hollow microballoon is 50ppm to concentration at 370 DEG C is 8.
Embodiment 2: take the block polymer polystyrene-poly oxygen ethene of 2.5g, be dissolved in the absolute ethyl alcohol of 30ml; Add the zinc acetate of 0.6g and the diethanol amine of 0.8ml, under room temperature, stir and within 3 hours, obtain zinc precursor liquid solution; The stannous chloride that takes 0.15g is placed in zinc precursor liquid solution, stirs 1 hour; Tin-zinc precursor solution is placed in to reactor, in 180 DEG C of reactions 24 hours; Use respectively alcohol and water centrifuge washing 3 times, obtain tin oxide-zinc oxide compound hollow microballoon; Microballoon is dissolved in and in absolute ethyl alcohol, obtains pastel; For alumina ceramic tube, deionized water, acetone, chloroform clean up, and dry, and tin oxide-zinc oxide compound hollow microballoon pastel is evenly coated in to earthenware surface, and welding electrode, encapsulation, obtain gas sensor. Utilize tin oxide-zinc oxide compound hollow microballoon diameter prepared by polystyrene-poly oxygen ethene to be distributed between 1.5～3 microns, the electrical response rate of the ethanol that is 50ppm to concentration at 370 DEG C is 5.4.
Embodiment 3: take the block polymer P123 of 2g, be dissolved in the deionized water of 30ml; Add the zinc acetate of 0.1g and the diethanol amine of 1ml, under room temperature, stir and within 3 hours, obtain zinc precursor liquid solution; The stannous chloride that takes 0.45g is placed in zinc precursor liquid solution, stirs 1 hour; Tin-zinc precursor solution is placed in to reactor, in 180 DEG C of reactions 24 hours; Use respectively alcohol and water centrifuge washing 3 times, obtain tin oxide-zinc oxide compound hollow microballoon; Microballoon is dissolved in and in absolute ethyl alcohol, obtains pastel; For alumina ceramic tube, deionized water, acetone, chloroform clean up, and dry, and tin oxide-zinc oxide compound hollow microballoon pastel is evenly coated in to earthenware surface, and welding electrode, encapsulation, obtain gas sensor. Change the ratio thus obtained microsphere distribution of sizes of tin and zinc in 2～3.5 micrometer ranges, gained ball wall is thinner, and broken microballoon is many, and the electrical response rate of the ethanol that is 50ppm to concentration at 370 DEG C is 8.5.
Embodiment 4: take the block polymer polystyrene-poly oxygen ethene of 2.5g, be dissolved in the deionized water of 30ml; Add the zinc chloride of 0.32g and the diethanol amine of 1ml, under room temperature, stir and within 4 hours, obtain zinc precursor liquid solution; The stannous chloride that takes 0.15g is placed in zinc precursor liquid solution, stirs 1 hour; Tin-zinc precursor solution is placed in to reactor, in 180 DEG C of reactions 12 hours; Use respectively alcohol and water centrifuge washing 3 times, obtain tin oxide-zinc oxide compound hollow microballoon; Microballoon is dissolved in and in absolute ethyl alcohol, obtains pastel; For alumina ceramic tube, deionized water, acetone, chloroform clean up, and dry, and tin oxide-zinc oxide compound hollow microballoon pastel is evenly coated in to earthenware surface, and welding electrode, encapsulation, obtain gas sensor. Changing zinc precursor body does not affect structure and the size of tin oxide-zinc oxide compound hollow microballoon, and the electrical response rate of gas sensor is constant.
Claims (2)
1. a preparation method for tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device, is characterized in that, comprises the steps:
(1) organic template is dissolved in organic solvent, after dissolving completely, adds the diethanol amine of zinc precursor body and 0.5 milliliter to 2.8 milliliters, or triethanolamine; Then at room temperature at least stir and within 3 hours, obtain zinc oxide precursor liquid solution;
Described organic template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (P123), or di-block copolymer polystyrene-poly oxygen ethene or softex kw;
Described organic solvent is a kind of or its combination in absolute ethyl alcohol, n-butanol, oxolane;
Described zinc precursor body is the one in two water zinc acetates, zinc chloride, zinc nitrate hexahydrate, Zinc vitriol;
(2) take tin presoma by tin presoma and zinc precursor body mol ratio 1:10～1:1, be placed in zinc precursor liquid solution, stir 2～4 hours, obtain tin-zinc compound precursor liquid solution;
Described tin presoma is stannic chloride, or stannous chloride;
The weight ratio of described zinc precursor body, organic template and organic solvent is 0.05～0.6:0.03～0.8:2～7;
(3) precursor solution is placed in to reactor, in 80～200 DEG C of reactions 12 hours to 24 hours;
(4) question response still temperature is down to room temperature, and milk-white coloured suspension is washed respectively 3～5 times with alcohol and water, obtains tin oxide-zinc oxide compound hollow microballoon, microballoon is placed in to alcohol or water is stand-by;
(5) for alumina ceramic tube, deionized water, acetone, chloroform clean up, dry for standby;
(6) suspension of tin oxide-zinc oxide compound hollow microballoon is evenly spread upon on alumina ceramic tube, earthenware is encapsulated;
(7) at 100～300 DEG C electricity aging 3～15 days, make tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device;
The described washing methods of step (4) is centrifugal under 5000 ~ 15000 revs/min of rotating speeds or suction filtration method all can;
The described aging atmosphere of step (7) is air.
2. tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device, is characterized in that, according to claim1Described method prepares.
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| CN104977320B (en) * | 2015-06-03 | 2017-11-14 | 安徽兰兮工程技术开发有限公司 | A kind of ceramic gas sensor for alcohol detection |
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| CN108828021A (en) * | 2018-05-03 | 2018-11-16 | 吉林大学 | Based on branching SnO2The alcohol gas sensor and preparation method thereof of/ZnO heterojunction structure sensitive material |
| CN108717072A (en) * | 2018-05-15 | 2018-10-30 | 大连理工大学 | A kind of light activated formaldehyde gas sensor and its preparation process |
| CN108627550A (en) * | 2018-05-18 | 2018-10-09 | 南京工业大学 | A kind of SnO2Adulterate preparation method and the application of the hydrogen sensing material of ZnO |
| CN109682867B (en) * | 2019-01-23 | 2022-05-24 | 陕西科技大学 | Micron-sized tin dioxide gas-sensitive material and preparation method and application thereof |
| CN111721813A (en) * | 2020-05-28 | 2020-09-29 | 西安电子科技大学 | Based on tubulose SnO2Array acetone gas sensor and preparation method thereof |
| CN112098463A (en) * | 2020-08-19 | 2020-12-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of fluorine modified nickel oxide/tin oxide composite sensor device, product and application thereof |
| CN112611786B (en) * | 2020-12-01 | 2023-04-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of graphene-loaded tin dioxide quantum dot for formaldehyde and nitrogen dioxide gas detection, product and application |
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