CN108535334A - A kind of methanol gas sensor preparation method of tin oxide nanoparticles and zinc oxide nanowire aggregate structure - Google Patents

A kind of methanol gas sensor preparation method of tin oxide nanoparticles and zinc oxide nanowire aggregate structure Download PDF

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CN108535334A
CN108535334A CN201810233857.6A CN201810233857A CN108535334A CN 108535334 A CN108535334 A CN 108535334A CN 201810233857 A CN201810233857 A CN 201810233857A CN 108535334 A CN108535334 A CN 108535334A
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composite material
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tin oxide
sensitive
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CN108535334B (en
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慈立杰
彭瑞芹
孙卿
陈靖桦
李德平
陈龙
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Shandong University
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    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles

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Abstract

The present invention relates to the methanol gas sensor preparation methods of a kind of tin oxide nanoparticles and zinc oxide nanowire aggregate structure, belong to the preparation field of the gas sensitive of gas sensor, and the present invention completes ZnO and SnO by simple chemically synthesized mode2The preparation of composite construction, after pass through controllable annealing process and obtain end product.The composite construction gives full play to the advantage of INVENTIONConventional metal-oxide gas sensitive, utilizes ZnO/SnO2Hetero-junctions regulates and controls air-sensitive performance, reduces operating temperature.The engineering reliability is high, repeats, and has excellent device stability.The brushing of high-precision silk screen printing machine is utilized after obtaining gas sensitive on a ceramic substrate, then in sensitive layer surface evaporation metal electrode；The contact for finally realizing sensitive layer and metal electrode based on the heterojunction structure, completes the preparation of methanol sensor.It is also with good stability while methanol sensor prepared by the present invention can realize highly sensitive detection and quick response at a temperature of 200 DEG C.

Description

A kind of methanol air-sensitive biography of tin oxide nanoparticles and zinc oxide nanowire aggregate structure Sensor preparation method
Technical field
The invention belongs to the preparation field of the gas sensitive of gas sensor more particularly to a kind of tin oxide nanoparticles and The methanol gas sensor preparation method of zinc oxide nanowire aggregate structure.
Background technology
From in the 1960s, Seiyama et al. develops flammable air-sensitive biography using metal-oxide semiconductor (MOS) for the first time After sensor, metal oxide base gas sensor is quickly grown, and is obtained extensively in civilian, industrial and three big field of environment measuring Application.Cut-off 2016, the sales volume of Metal Oxide Semiconductor Gas Sensing sensor accounts for the 57% of all sensors sales volume, The air range of the type sensor measurement is wide, low manufacture cost, simple in structure, response resume speed is fast, with other Departments of Electronics The hot spot that many advantages, such as good compatibility of uniting is studied as gas sensor.Common metal-oxide semiconductor (MOS) has SnO2、 ZnO、WO3、TiO2, NiO etc., wherein with SnO2, ZnO and WO3Gas-sensitive property be preferably widely used.SnO2, ZnO belongs to In n-type semiconductor oxide sensing material, the composite material based on this two kinds of materials is built, the ratio table of material is can effectively improve Area and surface-active site density, and the sensitivity of device can be improved by the hetero-junctions of formation.But in actual application, While requiring certain sensitivity, has quickly response also as one of the device performance paid close attention to, become air-sensitive biography One of key breakthrough direction of sensor application study.And specific assembling SnO2With two kinds of materials of ZnO, realize that synergistic effect improves gas Sensing device performance shortens response time great researching value.
Relative to traditional gas sensitive system, pass through specific assembling SnO2With two kinds of materials of ZnO, realize that synergistic effect improves Gas sensitive device performance shortens the response time, has more wide application prospect.For example, 106053556 A of patent application CN It discloses a kind of based on ZnO/SnO2The alcohol gas sensor of heterojunction structure composite material.The invention uses two one-step hydrothermal systems Obtain ZnO/SnO2Composite material sensitive material, utilizes ZnO/SnO2Between be formed by heterojunction structure and improve to the detection energy of ethyl alcohol Power, the pattern of the composite construction are the form of tiny balloon, provide the sensitivity of device.Under the conditions of operating temperature is 225 DEG C, The sensitivity of a concentration of 100ppm ethyl alcohol reaches 77.8, although obtaining preferable sensitivity, due to its response time is unknown It can not judge its response speed in detection process, it is relatively high to work at the same time temperature.
To sum up, the methanol sensor of prior art preparation still has the problems such as sensitivity is low, operating temperature is high, therefore, It is necessary to develop new methanol sensor, to further increase the detection performance and application value of methanol sensor.
Invention content
For the above-mentioned prior art the problem of, the present invention is intended to provide a kind of tin oxide nanoparticles and zinc oxide The methanol gas sensor preparation method of nanowire cluster poly structure, compared with prior art, methanol sensor prepared by the present invention It is also with good stability while capable of realizing highly sensitive detection and quick response at a temperature of 200 DEG C；In addition, this hair Bright preparation method is simple, controllable, production cost is low, is conducive to mass produce.
An object of the present invention is to provide a kind of with tin oxide nanoparticles and zinc oxide nanowire aggregate structure Composite material.
It is a kind of with tin oxide nanoparticles and zinc oxide nanowire aggregate structure the second object of the present invention is to provide The preparation method of composite material.
The third object of the present invention is to provide a kind of preparation method of methanol gas sensor.
The side that the fourth object of the present invention is to provide the preparation method of composite material of the present invention, prepares methanol gas sensor The application of method and its sensor of preparation.
For achieving the above object, the invention discloses following technical proposals：
First, the invention discloses a kind of composite woods with tin oxide nanoparticles and zinc oxide nanowire aggregate structure Material, the composite material are made of tin oxide nanoparticles and zinc oxide nanowire, and the nanoparticle aggregate is around nano wire Or be grown on nano wire, nano particle is presented in macro morphology and nano wire mutually winds the state of reunion.
Secondly, the invention discloses a kind of composite woods with tin oxide nanoparticles and zinc oxide nanowire aggregate structure The preparation method of material, specifically, the preparation method comprises the following steps：
1) tin source is dissolved in ethanol solution, is stirred, obtained homogeneous transparent solution, dimethylformamide is then added, obtains To mixed liquor, for use；The addition of dimethylformamide substance advantageously reduces the reunion of follow-up precursor species, reduces material and closes At grain size in the process；
2) zinc source is dissolved in ethanol solution, is stirred, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is mixed, is then added Alkaline matter adjusts pH value, obtains milky precursor solution；
4) synthesis of composite material：Hydrothermal synthesis is carried out to the milky precursor solution in step 3), after reaction Product is centrifuged ,-centrifugation-is then rinsed with ethyl alcohol and deionized water respectively and rinses, obtains gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, using two step seasonings It is annealed after drying to get the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure.
In step 1), the tin source includes：Stannic chloride pentahydrate (SnCl4·5H2O), two water butter of tin (SnCl2· 2H2O) etc..
In step 1), the volume ratio of the clear solution and dimethylformamide is 10-50:1.
Preferably, the volume ratio of the clear solution and dimethylformamide is 25:1.The preferred ratio is considered can Stannide is dissolved, meets the operability of later experiments, and the control of this ratio is associated with the foundation of the size of final product grain size, Obtain reproducible technique.
In step 2), the zinc source includes zinc chloride, anhydrous zinc acetate etc..
In step 3), the mixed proportion of the mixed liquor and clear solution is：Sn in mixed solution：The atomic ratio of Zn For 1-4:1.
In step 3), the alkaline matter includes NaOH, KOH etc..
In step 3), the adjustable range of the pH value is 8-10.
In step 4), the temperature of the hydrothermal synthesis is 160-200 DEG C, reaction time 6-24h.
Preferably, the temperature of the hydrothermal synthesis is 180 DEG C, reaction time 12h.
In step 4), the rotating speed of the centrifugation is that 4000-8000 turns/min, time 5-30min.
Preferably, the rotating speed of the centrifugation is 6000rpm/min, time 10min.
In step 5), the film thickness of the coating is 25 μm -200 μm.
Preferably, the film thickness of the coating is 100 μm.It, can be effective when the film thickness of coating is at 80 μm or more Reduce the generation of film surface crackle.
In step 5), the two steps seasoning is：Under vacuum environment, 3-5h is first dried at 80 DEG C, and 1- is then dried at 110 DEG C 3h。
In step 5), the annealing conditions are：Heating rate：10 DEG C/min, 1- is kept the temperature under 350-600 DEG C of nitrogen atmosphere Furnace cooling is to room temperature after 3h.
Again, the invention discloses a kind of methods of methanol gas sensor；Include the following steps：Utilize the photoetching of standard Technique, metal deposition technique composite material provided by the invention surface carry out Au electrodes deposition to get.
The thickness of the Au electrodes is 200nm, feature sizes≤0.5 μm.
Finally, the invention discloses the preparation method of composite material of the present invention and its composite material of preparation, prepare methanol Methanol gas prepared by application and the present invention of the method for gas sensor in sensor cell device and gas sensor array Application of the dependent sensor in gas in methanol detection.
Compared with prior art, the present invention achieves following advantageous effect：
(1) present invention has obtained having ZnO nano-wire and SnO using simple chemical synthesis mode2Nanoparticle agglomerates shape Composite construction enhance gas to effectively play high-specific surface area feature in addition to one-dimensional nano line and nano particle Adsorption capacity, improve device sensitivity.
(2) present invention synthesizes ZnO nano-wire and SnO by simple hydrothermal synthesis mode2Nanoparticle agglomerates shape structure, Nanoparticle agglomerates form a large amount of heterojunction around nano wire, can effectively improve the sensitivity of device, utilize this When the sensor that invention prepares composite material preparation can keep highly sensitive under 200 DEG C of operating temperature and quickly respond Between, and controllability is high, great application prospect.
(3) present invention is designed by rational material special appearance, different by building using the advantage of traditional gas sensitive Matter knot obtains highly sensitive methanol Sensitive Apparatus, and preparation process is repeatable, has larger application value.
(4) the also expansible formation gas sensor array of the technology of the present invention, technological operation are simple, controllable.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is the element manufacturing flow chart that the present invention makes methanol sensor.
Fig. 2 is the scanning electron microscope (SEM) photograph and high resolution electron microscopy figure of composite material prepared by the embodiment of the present invention 1；Wherein, (a), (b) it is the SEM figures under different multiples, is (c) that the TEM of (b) schemes.
Fig. 3 is the X-ray diffractogram of composite material prepared by 1-4 of the embodiment of the present invention.
Fig. 4 is sensitivity and 30ppm of the methanol sensor of the preparation of the embodiment of the present invention 1 in 1-100ppm concentration ranges The response time and recovery time of device under concentration.
Fig. 5 is stability test figure of the methanol sensor of the preparation of the embodiment of the present invention 1 when methanol concentration is 200ppm.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As described in background, the methanol sensor of prior art preparation still has that sensitivity is low, operating temperature is high The problems such as；Therefore, the present invention proposes the methanol gas sensor of kind of tin oxide nanoparticles and zinc oxide nanowire aggregate structure Preparation method；In conjunction with the drawings and specific embodiments, invention is further explained.
Embodiment 1
1, a kind of preparation method of the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, tool Body, the preparation method comprises the following steps：
1) SnCl is taken2·2H2O is dissolved in ethanol solution, stirs 50min, obtains homogeneous transparent solution, is then pressed described The volume ratio of bright solution and dimethylformamide is 25:Dimethylformamide is added in 1 ratio, obtains mixed liquor, for use；
2) it takes zinc chloride to be dissolved in ethanol solution, stirs 50min, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is pressed into mixed solution Middle Sn：The atomic ratio of Zn is 2:1 is mixed, and NaOH is then added, and solution ph is adjusted to 9, milky presoma is obtained Solution；
4) synthesis of composite material：Milky precursor solution in step 3) is fitted into polytetrafluoroethylene (PTFE) bottle, 180 Hydro-thermal reaction 12h at DEG C, after reaction centrifuges product, and rotating speed is controlled in 6000 turns/min, time 10min；Then It uses ethyl alcohol and deionized water to repeat flushing-centrifugation-flushing process 5 times respectively, obtains gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, what is obtained after coating is thin Film thickness control is 100 μm；Then there are the ceramics of film first to dry 4h at 80 DEG C above-mentioned load, 2h is then dried at 110 DEG C, after drying It anneals, heating rate control keeps the temperature 2h to get with tin oxide nano in 10 DEG C/min under 450 DEG C of nitrogen atmospheres The composite material of grain and zinc oxide nanowire aggregate structure.
2, a kind of method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill The surface for the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure that art obtains in the present embodiment The deposition of Au electrodes is carried out, the thickness of the Au electrodes is 200nm, and feature sizes are 0.5 μm.
Embodiment 2
1, a kind of preparation method of the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, tool Body, the preparation method comprises the following steps：
1) SnCl is taken2·2H2O is dissolved in ethanol solution, stirs 30min, obtains homogeneous transparent solution, is then pressed described The volume ratio of bright solution and dimethylformamide is 10:Dimethylformamide is added in 1 ratio, obtains mixed liquor, for use；
2) it takes zinc chloride to be dissolved in ethanol solution, stirs 30min, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is pressed into mixed solution Middle Sn：The atomic ratio of Zn is 1:1 is mixed, and NaOH is then added, and solution ph is adjusted to 8, milky presoma is obtained Solution；
4) synthesis of composite material：Milky precursor solution in step 3) is fitted into polytetrafluoroethylene (PTFE) bottle, 200 Hydro-thermal reaction 12h at DEG C, after reaction centrifuges product, and rotating speed is controlled in 4000 turns/min, time 5min；Then divide Not Yong ethyl alcohol and deionized water repeat flushing-centrifugation-flushing process 5 times, obtain gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, what is obtained after coating is thin Film thickness control is 200 μm；Then there are the ceramics of film first to dry 3h at 80 DEG C above-mentioned load, 1h is then dried at 110 DEG C, after drying It anneals, heating rate control keeps the temperature 1h to get with tin oxide nano in 10 DEG C/min under 350 DEG C of nitrogen atmospheres The composite material of grain and zinc oxide nanowire aggregate structure.
2, a kind of method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill The surface for the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure that art obtains in the present embodiment The deposition of Au electrodes is carried out, the thickness of the Au electrodes is 200nm, and feature sizes are 0.4 μm.
Embodiment 3
1, a kind of preparation method of the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, tool Body, the preparation method comprises the following steps：
1) SnCl is taken2·2H2O is dissolved in ethanol solution, stirs 50min, obtains homogeneous transparent solution, is then pressed described The volume ratio of bright solution and dimethylformamide is 50:Dimethylformamide is added in 1 ratio, obtains mixed liquor, for use；
2) it takes zinc chloride to be dissolved in ethanol solution, stirs 50min, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is pressed into mixed solution Middle Sn：The atomic ratio of Zn is 4:1 is mixed, and NaOH is then added, and solution ph is adjusted to 9, milky presoma is obtained Solution；
4) synthesis of composite material：Milky precursor solution in step 3) is fitted into polytetrafluoroethylene (PTFE) bottle, 160 Hydro-thermal reaction 12h at DEG C, after reaction centrifuges product, and rotating speed is controlled in 5000 turns/min, time 10min；Then It uses ethyl alcohol and deionized water to repeat flushing-centrifugation-flushing process 5 times respectively, obtains gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, what is obtained after coating is thin Film thickness control is 25 μm；Then there are the ceramics of film first to dry 5h at 80 DEG C above-mentioned load, 3h is then dried at 110 DEG C, after drying It anneals, heating rate control keeps the temperature 3h to get with tin oxide nano in 10 DEG C/min under 600 DEG C of nitrogen atmospheres The composite material of grain and zinc oxide nanowire aggregate structure.
2, a kind of method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill The surface for the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure that art obtains in the present embodiment The deposition of Au electrodes is carried out, the thickness of the Au electrodes is 200nm, and feature sizes are 0.2 μm.
Embodiment 4
1, a kind of preparation method of the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, tool Body, the preparation method comprises the following steps：
1) SnCl is taken4·4H2O is dissolved in ethanol solution, stirs 50min, obtains homogeneous transparent solution, is then pressed described The volume ratio of bright solution and dimethylformamide is 40:Dimethylformamide is added in 1 ratio, obtains mixed liquor, for use；
2) it takes anhydrous zinc acetate to be dissolved in ethanol solution, stirs 50min, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is pressed into mixed solution Middle Sn：The atomic ratio of Zn is 3:1 is mixed, and KOH is then added, and solution ph is adjusted to 10, milky presoma is obtained Solution；
4) synthesis of composite material：Milky precursor solution in step 3) is fitted into polytetrafluoroethylene (PTFE) bottle, 200 Hydro-thermal reaction 6h at DEG C, after reaction centrifuges product, and rotating speed is controlled in 8000 turns/min, time 30min；Then divide Not Yong ethyl alcohol and deionized water repeat flushing-centrifugation-flushing process 5 times, obtain gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, what is obtained after coating is thin Film thickness control is 150 μm；Then there are the ceramics of film first to dry 4h at 80 DEG C above-mentioned load, 3h is then dried at 110 DEG C, after drying It anneals, heating rate control keeps the temperature 1h to get with tin oxide nano in 10 DEG C/min under 550 DEG C of nitrogen atmospheres The composite material of grain and zinc oxide nanowire aggregate structure.
2, a kind of method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill The surface for the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure that art obtains in the present embodiment The deposition of Au electrodes is carried out, the thickness of the Au electrodes is 200nm, and feature sizes are 0.1 μm.
Embodiment 5
1, a kind of preparation method of the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, tool Body, the preparation method comprises the following steps：
1) SnCl is taken4·4H2O is dissolved in ethanol solution, stirs 60min, obtains homogeneous transparent solution, is then pressed described The volume ratio of bright solution and dimethylformamide is 45:Dimethylformamide is added in 1 ratio, obtains mixed liquor, for use；
2) it takes anhydrous zinc acetate to be dissolved in ethanol solution, stirs 50min, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is pressed into mixed solution Middle Sn：The atomic ratio of Zn is 3:1 is mixed, and KOH is then added, and solution ph is adjusted to 8, it is molten to obtain milky presoma Liquid；
4) synthesis of composite material：Milky precursor solution in step 3) is fitted into polytetrafluoroethylene (PTFE) bottle, 160 Hydro-thermal reaction for 24 hours, after reaction centrifuges product at DEG C, and rotating speed is controlled in 7000 turns/min, time 20min；Then It uses ethyl alcohol and deionized water to repeat flushing-centrifugation-flushing process 5 times respectively, obtains gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, what is obtained after coating is thin Film thickness control is 150 μm；Then there are the ceramics of film first to dry 2h at 80 DEG C above-mentioned load, 2h is then dried at 110 DEG C, after drying It anneals, heating rate control keeps the temperature 3h to get with tin oxide nano in 10 DEG C/min under 400 DEG C of nitrogen atmospheres The composite material of grain and zinc oxide nanowire aggregate structure.
2, a kind of method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill The surface for the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure that art obtains in the present embodiment The deposition of Au electrodes is carried out, the thickness of the Au electrodes is 200nm, and feature sizes are 0.05 μm.
Performance test：
Composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure prepared by embodiment 1 is carried out Microexamination, the results are shown in Figure 2, as can be seen from Figure 2：The composite material is by tin oxide nanoparticles and zinc-oxide nano Line is constituted, and existing state is nanoparticle aggregate around nano wire or is grown on nano wire, and macro morphology presentation is received Rice grain and nano wire mutually wind the state of reunion, are formed and contact good hetero-junctions.Tin oxide nanoparticles size is about Between 5-10 nanometers, zinc-oxide nano dimensions are about in 5 rans, and length is in 10-100 rans.This is multiple The gas-sensitive property of device can be improved in conjunction with nanostructure high-specific surface area feature and the regulation and control advantage of hetero-junctions by closing structure.It is right Methanol gas sensor prepared by embodiment 1-4 carries out XRD tests, and the results are shown in Figure 3, as can be seen from Figure 3：Pass through regulation and control Zn and Sn atomic ratios determine best compositive relation, form the form that nano particle is reunited with nano wire winding.Additionally by XRD tests can determine that product is the mixture of tin oxide and tin oxide.The crystal structure of tin oxide and JCPDF41-1445 phases Unanimously, the crystal structure of zinc oxide is consistent with JCPDF05-0664.Air-sensitive is carried out to methanol gas sensor prepared by embodiment 1 The test of performance, as a result as shown in Figures 4 and 5.As can be seen from Figure 4：Worked based on the sensor of the composite construction at 200 DEG C temperature Under degree, may be implemented to gas concentration 1ppm-100ppm highly sensitive quick response.When gas concentration is 30ppm, device Response time and recovery time are respectively 6s and 168s, show faster air-sensitive response speed.As can be seen from Figure 5：It is based on The sensor of the composite construction is under 200 DEG C of operating temperatures, and gas concentration is at 200ppm, in 6 cyclical stabilities are tested Whole fluctuation rate is less than 5%, and device presents good stability.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for those skilled in the art For member, the application can have various modifications and variations.Any modification made by within the spirit and principles of this application, Equivalent replacement, improvement etc., should be included within the protection domain of the application.

Claims (10)

1. a kind of composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure, it is characterised in that：It is described Composite material is made of tin oxide nanoparticles and zinc oxide nanowire, and the nanoparticle aggregate is around nano wire or grows In on nano wire, nano particle is presented in macro morphology and nano wire mutually winds the state of reunion.
2. the preparation method of composite material as described in claim 1, it is characterised in that：The preparation method includes following step Suddenly：
1) tin source is dissolved in ethanol solution, is stirred, obtained homogeneous transparent solution, dimethylformamide is then added, is mixed Liquid is closed, for use；The addition of dimethylformamide substance advantageously reduces the reunion of follow-up precursor species, reduces materials synthesis mistake Grain size in journey；
2) zinc source is dissolved in ethanol solution, is stirred, obtain homogeneous transparent solution, for use；
3) precursor solution is configured：Clear solution in mixed liquor and step 2) in step 1) is mixed, alkalinity is then added Substance adjusts pH value, obtains milky precursor solution；
4) synthesis of composite material：Hydrothermal synthesis is carried out to the milky precursor solution in step 3), it after reaction will production Object centrifuges, and is then rinsed-centrifugation-with ethyl alcohol and deionized water respectively and rinses, and obtains gum-like product；
5) screen process press is utilized, the gum-like product in step 4) is coated to ceramic substrate, is dried using two step seasonings It is annealed afterwards to get the composite material with tin oxide nanoparticles and zinc oxide nanowire aggregate structure.
3. the preparation method of composite material as described in claim 1, it is characterised in that：The tin source includes：Five water, four chlorination Tin, two water butters of tin；The zinc source includes zinc chloride, anhydrous zinc acetate.
4. the preparation method of composite material as described in claim 1, it is characterised in that：In step 1), the clear solution and The volume ratio of dimethylformamide is 10-50:1；
Preferably, the volume ratio of the clear solution and dimethylformamide is 25:1.
5. the preparation method of composite material as described in claim 1, it is characterised in that：In step 3), the mixed liquor and thoroughly The mixed proportion of bright solution is：Sn in mixed solution：The atomic ratio of Zn is 1-4:1.
6. the preparation method of composite material as described in claim 1, it is characterised in that：In step 3), the alkaline matter packet Include NaOH or KOH；The adjustable range of the pH value is 8-10.
7. the preparation method of composite material as described in claim 1, it is characterised in that：In step 4), the hydrothermal synthesis Temperature is 160-200 DEG C, reaction time 6-24h；The rotating speed of the centrifugation is that 4000-8000 turns/min, time 5- 30min；
Preferably, the temperature of the hydrothermal synthesis is 180 DEG C, reaction time 12h；
Preferably, the rotating speed of the centrifugation is 6000rpm/min, time 10min；
Preferably, in step 5), the film thickness of the coating is 25 μm -200 μm；
It is further preferred that the film thickness of the coating is 100 μm.
8. the preparation method of composite material as described in claim 1, it is characterised in that：In step 5), the two steps seasoning For：Under vacuum environment, 3-5h is first dried at 80 DEG C, and 1-3h is then dried at 110 DEG C；The annealing conditions are：Heating rate：10℃/ Min, furnace cooling is to room temperature after keeping the temperature 1-3h under 350-600 DEG C of nitrogen atmosphere.
9. a kind of preparation method of methanol gas sensor；Include the following steps：Utilize the photoetching process of standard, metal deposit skill Art composite material surface as described in claim 1 carry out Au electrodes deposition to get；Preferably, the thickness of the Au electrodes For 200nm, feature sizes≤0.5 μm.
10. composite material as described in claim 1, such as the preparation method of claim 2-8 any one of them composite materials, The application of methanol gas sensor prepared by preparation method as claimed in claim 9 in methanol gas detection.
CN201810233857.6A 2018-03-21 2018-03-21 Preparation method of methanol gas sensor with tin oxide nano-particles and zinc oxide nano-wire agglomeration structure Active CN108535334B (en)

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Cited By (4)

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CN109813760A (en) * 2019-02-28 2019-05-28 江苏理工学院 A kind of zinc oxide nanowire gas sensor and preparation method thereof
CN110040766A (en) * 2019-04-02 2019-07-23 重庆大学 The gas-sensitive nano material and gas sensor of high moisture resistance
CN110589875A (en) * 2019-09-17 2019-12-20 复旦大学 Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof
CN111272825A (en) * 2020-03-06 2020-06-12 电子科技大学中山学院 Metal oxide gas sensor based on surface plasmon enhancement

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109813760A (en) * 2019-02-28 2019-05-28 江苏理工学院 A kind of zinc oxide nanowire gas sensor and preparation method thereof
CN110040766A (en) * 2019-04-02 2019-07-23 重庆大学 The gas-sensitive nano material and gas sensor of high moisture resistance
CN110040766B (en) * 2019-04-02 2021-09-03 重庆大学 Preparation method of high-humidity-resistance nano gas-sensitive material and gas-sensitive sensor
CN110589875A (en) * 2019-09-17 2019-12-20 复旦大学 Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof
CN110589875B (en) * 2019-09-17 2021-10-26 复旦大学 Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof
CN111272825A (en) * 2020-03-06 2020-06-12 电子科技大学中山学院 Metal oxide gas sensor based on surface plasmon enhancement

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