CN108535334B - Preparation method of methanol gas sensor with tin oxide nano-particles and zinc oxide nano-wire agglomeration structure - Google Patents
Preparation method of methanol gas sensor with tin oxide nano-particles and zinc oxide nano-wire agglomeration structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a methanol gas sensor with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires, belonging to the field of preparation of gas sensitive materials of gas sensors2And preparing the composite structure, and then obtaining a final product through a controllable annealing process. The composite structure fully exerts the advantages of the traditional metal oxide gas-sensitive material and utilizes ZnO/SnO2The heterojunction regulates and controls the gas-sensitive performance and reduces the working temperature. The technology has high reliability, repeatability and excellent device stability. Coating the obtained gas-sensitive material on a ceramic substrate by using a high-precision screen printing machine, and then evaporating a metal electrode on the surface of the sensitive layer; and finally, the sensitive layer based on the heterojunction structure is contacted with the metal electrode, and the preparation of the methanol sensor is completed. The methanol sensor prepared by the invention can realize high-sensitivity detection and quick response at the temperature of 200 ℃, and has good stability.
Description
Technical Field
The invention belongs to the field of preparation of gas sensitive materials of gas sensors, and particularly relates to a preparation method of a methanol gas sensor with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires.
Background
Since the 60 s of the 20 th century, after Seiyama et al developed a combustible gas sensor by using a metal oxide semiconductor for the first time, the metal oxide-based gas sensor developed rapidly and was widely applied to three fields of civil use, industry and environmental detection. In 2016, the sales of the metal oxide semiconductor gas sensor accounts for 57% of the sales of all sensors, and the metal oxide semiconductor gas sensor has the advantages of wide gas measurement range, low manufacturing cost, simple structure, high response recovery speed, good compatibility with other electronic systems and the like, and becomes a hot point for research of the gas sensor. A common metal oxide semiconductor is SnO2、ZnO、WO3、TiO2NiO, etc., wherein SnO2ZnO and WO3The gas-sensitive properties of (b) are preferably widely used. SnO2ZnO belongs to n-type semiconductor oxidationThe object sensing material is a composite material based on the two materials, so that the specific surface area and the surface active site density of the material can be effectively improved, and the sensitivity of a device can be improved through a formed heterojunction. However, in practical applications, while a certain sensitivity is required, a fast response is one of the important device performances, and becomes one of the key breakthrough directions for the application research of the gas sensor. While the specific assembly SnO2And ZnO, the synergistic effect is realized, the performance of the gas sensitive device is improved, and the response time is shortened, so that the gas sensitive device has a great research value.
Compared with the traditional gas-sensitive material system, the SnO is specifically assembled2And ZnO, the performance of the gas sensitive device is improved by realizing synergistic effect, the response time is shortened, and the gas sensitive device has wider application prospect. For example, patent application CN 106053556A discloses a ZnO/SnO-based catalyst2Alcohol gas sensor of heterostructure combined material. The invention prepares ZnO/SnO by using a two-step hydrothermal method2Composite material sensitive material using ZnO/SnO2The heterogeneous structure formed between the two layers improves the detection capability of ethanol, and the shape of the composite structure is in the form of hollow microspheres, so that the sensitivity of the device is improved. When the working temperature is 225 ℃, the sensitivity of ethanol with the concentration of 100ppm reaches 77.8, although good sensitivity is obtained, the response time is unknown, so that the response speed of the ethanol in the detection process cannot be judged, and the working temperature is relatively high.
In summary, the methanol sensor prepared by the prior art still has the problems of low sensitivity, high working temperature and the like, so that it is necessary to develop a new methanol sensor to further improve the detection performance and application value of the methanol sensor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a methanol gas sensor with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires, and compared with the prior art, the prepared methanol sensor can realize high-sensitivity detection and quick response at the temperature of 200 ℃, and has good stability; in addition, the preparation method is simple and controllable, has low production cost and is beneficial to large-scale production.
One of the purposes of the invention is to provide a composite material with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires.
The second purpose of the invention is to provide a preparation method of the composite material with the agglomerated structure of the tin oxide nano-particles and the zinc oxide nano-wires.
The invention also aims to provide a preparation method of the methanol gas sensor.
The fourth purpose of the invention is to provide a preparation method of the composite material, a method for preparing a methanol gas sensor and application of the sensor prepared by the method.
In order to realize the purpose, the invention discloses the following technical scheme:
the invention discloses a composite material with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires, which comprises the tin oxide nano-particles and the zinc oxide nano-wires, wherein the nano-particles are aggregated around the nano-wires or grow on the nano-wires, and the macroscopic morphology of the composite material is in a state that the nano-particles and the nano-wires are mutually wound and agglomerated.
The invention further discloses a preparation method of the composite material with the tin oxide nano-particles and the zinc oxide nano-wire agglomeration structure, and the preparation method comprises the following steps:
1) dissolving a tin source in an ethanol solution, stirring to obtain a uniform and transparent solution, and then adding dimethylformamide to obtain a mixed solution for later use; the addition of the dimethyl formamide substance is beneficial to reducing the agglomeration of the subsequent precursor substance and reducing the grain size in the material synthesis process;
2) dissolving a zinc source in an ethanol solution, and stirring to obtain a uniform and transparent solution for later use;
3) preparing a precursor solution: mixing the mixed solution obtained in the step 1) with the transparent solution obtained in the step 2), adding an alkaline substance, and adjusting the pH value to obtain a milky precursor solution;
4) synthesis of the composite material: carrying out hydro-thermal synthesis on the milky white precursor solution in the step 3), carrying out centrifugal separation on a product after the reaction is finished, and then respectively carrying out washing-centrifugation-washing on the product by using ethanol and deionized water to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, drying by adopting a two-step drying method, and then annealing to obtain the composite material with the aggregation structure of the tin oxide nano-particles and the zinc oxide nano-wires.
In step 1), the tin source includes: tin tetrachloride pentahydrate (SnCl)4·5H2O), tin tetrachloride dihydrate (SnCl)2·2H2O), and the like.
In the step 1), the volume ratio of the transparent solution to the dimethylformamide is 10-50: 1.
Preferably, the volume ratio of the transparent solution to the dimethylformamide is 25: 1. The optimized proportion considers the soluble stannide, meets the operability of later experiments, and establishes the relation between the proportion control and the size of the particle size of the final product, thereby obtaining a reproducible process.
In the step 2), the zinc source comprises zinc chloride, anhydrous zinc acetate and the like.
In the step 3), the mixing ratio of the mixed solution and the transparent solution is as follows: sn in the mixed solution: the atomic ratio of Zn is 1-4: 1.
In the step 3), the alkaline substance comprises NaOH, KOH and the like.
In the step 3), the adjusting range of the pH value is 8-10.
In the step 4), the temperature of the hydrothermal synthesis is 160-200 ℃, and the reaction time is 6-24 h.
Preferably, the temperature of the hydrothermal synthesis is 180 ℃, and the reaction time is 12 h.
In the step 4), the rotation speed of the centrifugal separation is 4000-8000 rpm, and the time is 5-30 min.
Preferably, the rotation speed of the centrifugal separation is 6000rpm/min, and the time is 10 min.
In step 5), the thickness of the coated film is 25-200 μm.
Preferably, the coated film has a thickness of 100 μm. When the thickness of the coated film is more than 80 μm, the generation of cracks on the surface of the film can be effectively reduced.
In the step 5), the two-step drying method comprises the following steps: baking at 80 deg.C for 3-5 hr under vacuum, and baking at 110 deg.C for 1-3 hr.
In the step 5), the annealing conditions are as follows: temperature rise rate: 10 ℃/min, preserving the heat for 1-3h in the nitrogen atmosphere at the temperature of 350-600 ℃, and then slowly cooling to the room temperature along with the furnace.
Thirdly, the invention discloses a method for preparing the methanol gas sensor; the method comprises the following steps: and depositing an Au electrode on the surface of the composite material by using a standard photoetching process and a metal deposition technology to obtain the composite material.
The thickness of the Au electrode is 200nm, and the line width is less than or equal to 0.5 mu m.
Finally, the invention discloses a preparation method of the composite material, the composite material prepared by the preparation method, application of the method for preparing the methanol gas sensor in a sensor unit device and a gas sensor array, and application of the methanol gas sensor prepared by the preparation method in methanol detection.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention obtains ZnO nano-wires and SnO by utilizing a simple chemical synthesis mode2The nano-particle is in an aggregated composite structure, so that the characteristic of high specific surface area of the nano-particles and the one-dimensional nano-wires is effectively exerted, the adsorption capacity of gas is enhanced, and the sensitivity of the device is improved.
(2) The invention synthesizes ZnO nano-wire and SnO through a simple hydrothermal synthesis mode2The sensor prepared by the composite material can keep high sensitivity and quick response time at the working temperature of 200 ℃, has high controllability and has great application prospect.
(3) The invention obtains the methanol sensitive device with high sensitivity by constructing the heterojunction by means of reasonable material special shape design and utilizing the advantages of the traditional gas sensitive material, and the preparation process can be repeated and has larger application value.
(4) The technology of the invention can also be expanded to form a gas sensor array, and the process operation is simple and controllable.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a flow chart of the device for manufacturing a methanol sensor according to the present invention.
FIG. 2 is a scanning electron microscope image and a high resolution electron microscope image of the composite material prepared in example 1 of the present invention; wherein, (a) and (b) are SEM images at different magnification, and (c) is a TEM image of (b).
FIG. 3 is an X-ray diffraction pattern of composites prepared in examples 1-4 of the present invention.
FIG. 4 is a graph showing the sensitivity of a methanol sensor prepared in example 1 of the present invention in the range of 1-100ppm concentration and the response time and recovery time of the device at 30ppm concentration.
FIG. 5 is a stability test chart of the methanol sensor prepared in example 1 of the present invention at a methanol concentration of 200 ppm.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the methanol sensor prepared by the prior art still has the problems of low sensitivity, high working temperature and the like; therefore, the invention provides a preparation method of a methanol gas sensor with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires; the invention will now be further described with reference to the accompanying drawings and detailed description.
Example 1
1. A preparation method of a composite material with a tin oxide nanoparticle and zinc oxide nanowire agglomerated structure comprises the following steps:
1) taking SnCl2·2H2Dissolving O in an ethanol solution, stirring for 50min to obtain a uniform transparent solution, and then adding dimethylformamide according to the volume ratio of the transparent solution to the dimethylformamide of 25:1 to obtain a mixed solution for later use;
2) dissolving zinc chloride in ethanol solution, stirring for 50min to obtain uniform transparent solution;
3) preparing a precursor solution: mixing the mixed solution in the step 1) and the transparent solution in the step 2) according to the ratio of Sn: mixing Zn at an atomic ratio of 2:1, adding NaOH, and adjusting the pH value of the solution to 9 to obtain a milky precursor solution;
4) synthesis of the composite material: filling the milky white precursor solution in the step 3) into a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 12h at 180 ℃, and after the reaction is finished, carrying out centrifugal separation on a product, wherein the rotating speed is controlled at 6000 revolutions per minute for 10 min; then, repeatedly washing, centrifuging and washing with ethanol and deionized water for 5 times to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, and controlling the thickness of the film obtained after coating to be 100 micrometers; and then, drying the ceramic loaded with the film at 80 ℃ for 4h, then at 110 ℃ for 2h, annealing after drying, controlling the temperature rise speed at 10 ℃/min, and keeping the temperature at 450 ℃ for 2h in a nitrogen atmosphere to obtain the composite material with the tin oxide nano-particles and zinc oxide nano-wire agglomeration structure.
2. A method of a methanol gas sensor; the method comprises the following steps: the standard photolithography process and metal deposition technique were used to deposit an Au electrode on the surface of the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires obtained in this example, where the thickness of the Au electrode was 200nm and the wire width was 0.5 μm.
Example 2
1. A preparation method of a composite material with a tin oxide nanoparticle and zinc oxide nanowire agglomerated structure comprises the following steps:
1) taking SnCl2·2H2Dissolving O in an ethanol solution, stirring for 30min to obtain a uniform transparent solution, and then adding dimethylformamide according to the volume ratio of the transparent solution to the dimethylformamide of 10:1 to obtain a mixed solution for later use;
2) dissolving zinc chloride in ethanol solution, stirring for 30min to obtain uniform transparent solution;
3) preparing a precursor solution: mixing the mixed solution in the step 1) and the transparent solution in the step 2) according to the ratio of Sn: mixing Zn at the atomic ratio of 1:1, adding NaOH, and adjusting the pH value of the solution to 8 to obtain a milky precursor solution;
4) synthesis of the composite material: filling the milky white precursor solution in the step 3) into a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 12h at 200 ℃, and after the reaction is finished, carrying out centrifugal separation on the product, wherein the rotating speed is controlled at 4000 revolutions per minute for 5 min; then, repeatedly washing, centrifuging and washing with ethanol and deionized water for 5 times to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, and controlling the thickness of the film obtained after coating to be 200 mu m; and then, drying the ceramic loaded with the film at 80 ℃ for 3h, then at 110 ℃ for 1h, annealing after drying, controlling the temperature rise speed at 10 ℃/min, and keeping the temperature at 350 ℃ for 1h in a nitrogen atmosphere to obtain the composite material with the tin oxide nano-particles and zinc oxide nano-wire agglomeration structure.
2. A method of a methanol gas sensor; the method comprises the following steps: the standard photolithography process and metal deposition technique were used to deposit an Au electrode on the surface of the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires obtained in this example, where the thickness of the Au electrode was 200nm and the wire width was 0.4 μm.
Example 3
1. A preparation method of a composite material with a tin oxide nanoparticle and zinc oxide nanowire agglomerated structure comprises the following steps:
1) taking SnCl2·2H2Dissolving O in an ethanol solution, stirring for 50min to obtain a uniform transparent solution, and then adding dimethylformamide according to the volume ratio of the transparent solution to the dimethylformamide of 50:1 to obtain a mixed solution for later use;
2) dissolving zinc chloride in ethanol solution, stirring for 50min to obtain uniform transparent solution;
3) preparing a precursor solution: mixing the mixed solution in the step 1) and the transparent solution in the step 2) according to the ratio of Sn: mixing Zn at an atomic ratio of 4:1, adding NaOH, and adjusting the pH value of the solution to 9 to obtain a milky precursor solution;
4) synthesis of the composite material: filling the milky white precursor solution in the step 3) into a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 12 hours at 160 ℃, and after the reaction is finished, carrying out centrifugal separation on the product, wherein the rotating speed is controlled at 5000 r/min and the time is 10 min; then, repeatedly washing, centrifuging and washing with ethanol and deionized water for 5 times to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, and controlling the thickness of the film obtained after coating to be 25 micrometers; and then, drying the ceramic loaded with the film at 80 ℃ for 5h, then at 110 ℃ for 3h, annealing after drying, controlling the temperature rise speed at 10 ℃/min, and keeping the temperature at 600 ℃ for 3h in a nitrogen atmosphere to obtain the composite material with the tin oxide nano-particles and zinc oxide nano-wire agglomeration structure.
2. A method of a methanol gas sensor; the method comprises the following steps: the standard photolithography process and metal deposition technology were used to deposit an Au electrode on the surface of the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires obtained in this example, where the thickness of the Au electrode was 200nm and the wire width was 0.2 μm.
Example 4
1. A preparation method of a composite material with a tin oxide nanoparticle and zinc oxide nanowire agglomerated structure comprises the following steps:
1) taking SnCl4·4H2Dissolving O in an ethanol solution, stirring for 50min to obtain a uniform transparent solution, and then adding dimethylformamide according to the volume ratio of the transparent solution to the dimethylformamide of 40:1 to obtain a mixed solution for later use;
2) dissolving anhydrous zinc acetate in ethanol solution, and stirring for 50min to obtain uniform transparent solution;
3) preparing a precursor solution: mixing the mixed solution in the step 1) and the transparent solution in the step 2) according to the ratio of Sn: mixing Zn at the atomic ratio of 3:1, adding KOH, and adjusting the pH value of the solution to 10 to obtain a milky precursor solution;
4) synthesis of the composite material: filling the milky white precursor solution in the step 3) into a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 6h at 200 ℃, and after the reaction is finished, carrying out centrifugal separation on a product, wherein the rotating speed is controlled at 8000 revolutions per minute for 30 min; then, repeatedly washing, centrifuging and washing with ethanol and deionized water for 5 times to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, and controlling the thickness of the film obtained after coating to be 150 micrometers; and then, drying the ceramic loaded with the film at 80 ℃ for 4h, then at 110 ℃ for 3h, annealing after drying, controlling the temperature rise speed at 10 ℃/min, and preserving heat for 1h at 550 ℃ in a nitrogen atmosphere to obtain the composite material with the tin oxide nano-particles and zinc oxide nano-wire agglomeration structure.
2. A method of a methanol gas sensor; the method comprises the following steps: the standard photolithography process and metal deposition technique were used to deposit an Au electrode on the surface of the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires obtained in this example, where the thickness of the Au electrode was 200nm and the wire width was 0.1 μm.
Example 5
1. A preparation method of a composite material with a tin oxide nanoparticle and zinc oxide nanowire agglomerated structure comprises the following steps:
1) taking SnCl4·4H2Dissolving O in an ethanol solution, stirring for 60min to obtain a uniform transparent solution, and then adding dimethylformamide according to the volume ratio of the transparent solution to the dimethylformamide of 45:1 to obtain a mixed solution for later use;
2) dissolving anhydrous zinc acetate in ethanol solution, and stirring for 50min to obtain uniform transparent solution;
3) preparing a precursor solution: mixing the mixed solution in the step 1) and the transparent solution in the step 2) according to the ratio of Sn: mixing Zn at the atomic ratio of 3:1, adding KOH, and adjusting the pH value of the solution to 8 to obtain a milky precursor solution;
4) synthesis of the composite material: filling the milky white precursor solution in the step 3) into a polytetrafluoroethylene bottle, carrying out hydrothermal reaction at 160 ℃ for 24h, and after the reaction is finished, carrying out centrifugal separation on a product, wherein the rotating speed is controlled at 7000 r/min and the time is 20 min; then, repeatedly washing, centrifuging and washing with ethanol and deionized water for 5 times to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, and controlling the thickness of the film obtained after coating to be 150 micrometers; and then, drying the ceramic loaded with the film at 80 ℃ for 2h, then at 110 ℃ for 2h, annealing after drying, controlling the temperature rise speed at 10 ℃/min, and keeping the temperature for 3h under the nitrogen atmosphere at 400 ℃ to obtain the composite material with the tin oxide nano-particles and zinc oxide nano-wire agglomeration structure.
2. A method of a methanol gas sensor; the method comprises the following steps: the standard photolithography process and metal deposition technology were used to deposit an Au electrode on the surface of the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires obtained in this example, where the thickness of the Au electrode was 200nm and the wire width was 0.05 μm.
And (3) performance testing:
microscopic observation was performed on the composite material having the agglomerated structure of tin oxide nanoparticles and zinc oxide nanowires prepared in example 1, and the results are shown in fig. 2, from which it can be seen that: the composite material is composed of tin oxide nano-particles and zinc oxide nano-wires, wherein the existing state is that the nano-particles are gathered around the nano-wires or grow on the nano-wires, and the macro morphology presents the state that the nano-particles and the nano-wires are mutually wound and agglomerated, so that a heterojunction with good contact is formed. The size of tin oxide nano-particles is about 5-10 nanometers, the diameter of zinc oxide nano-wires is about 5 nanometers, and the length is about 10-100 nanometers. The composite structure can combine the high specific surface area characteristic of the nano structure and the regulation and control advantages of the heterojunction, and improve the gas-sensitive characteristic of the device. XRD measurements were performed on the methanol gas sensors prepared in examples 1 to 4, and the results are shown in FIG. 3, from which it can be seen that: the optimal composite relationship is determined by regulating the atomic ratio of Zn to Sn, and the winding and agglomeration form of the nano particles and the nano wires is formed. The product can additionally be determined by XRD testing to be a mixture of tin oxide and tin oxide. The crystal structure of tin oxide is consistent with JCPDF41-1445, and the crystal structure of zinc oxide is consistent with JCPDF 05-0664. The methanol gas sensor prepared in example 1 was subjected to gas sensing performance test, and the results are shown in fig. 4 and 5. As can be seen from fig. 4: the sensor based on the composite structure can realize high-sensitivity quick response to gas concentration of 1ppm-100ppm at the working temperature of 200 ℃. When the gas concentration is 30ppm, the response time and the recovery time of the device are respectively 6s and 168s, and the gas sensitive response speed is higher. As can be seen from fig. 5: the sensor based on the composite structure has the advantages that the overall fluctuation rate is lower than 5% in 6 cycle stability tests when the gas concentration is 200ppm at the working temperature of 200 ℃, and the device has good stability.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (14)
1. A preparation method of a composite material with an agglomerated structure of tin oxide nano-particles and zinc oxide nano-wires is characterized by comprising the following steps: the composite material is composed of tin oxide nano-particles and zinc oxide nano-wires, the nano-particles are gathered around the nano-wires or grow on the nano-wires, and the macro-morphology shows the state that the nano-particles and the nano-wires are mutually wound and agglomerated;
the preparation method comprises the following steps:
1) dissolving a tin source in an ethanol solution, stirring to obtain a uniform and transparent solution, and then adding dimethylformamide to obtain a mixed solution for later use; the addition of the dimethyl formamide substance is beneficial to reducing the agglomeration of the subsequent precursor substance and reducing the grain size in the material synthesis process;
2) dissolving a zinc source in an ethanol solution, and stirring to obtain a uniform and transparent solution for later use;
3) preparing a precursor solution: mixing the mixed solution obtained in the step 1) with the transparent solution obtained in the step 2), adding an alkaline substance, and adjusting the pH value to obtain a milky precursor solution;
4) synthesis of the composite material: carrying out hydro-thermal synthesis on the milky white precursor solution in the step 3), carrying out centrifugal separation on a product after the reaction is finished, and then respectively carrying out washing-centrifugation-washing on the product by using ethanol and deionized water to obtain a colloidal product;
5) coating the colloidal product obtained in the step 4) on a ceramic substrate by using a screen printer, drying by adopting a two-step drying method, and then annealing to obtain the composite material with the aggregation structure of the tin oxide nano-particles and the zinc oxide nano-wires.
2. A method of preparing a composite material according to claim 1, wherein: the tin source includes: tin tetrachloride pentahydrate or tin tetrachloride dihydrate; the zinc source comprises zinc chloride or anhydrous zinc acetate.
3. A method of preparing a composite material according to claim 1, wherein: in the step 1), the volume ratio of the transparent solution to the dimethylformamide is 10-50: 1.
4. A method of preparing a composite material according to claim 3, wherein: the volume ratio of the clear solution to dimethylformamide was 25: 1.
5. A method of preparing a composite material according to claim 1, wherein: in the step 3), the mixing ratio of the mixed solution and the transparent solution is as follows: sn in the mixed solution: the atomic ratio of Zn is 1-4: 1.
6. A method of preparing a composite material according to claim 1, wherein: in the step 3), the alkaline substance comprises NaOH or KOH; the pH value is adjusted within the range of 8-10.
7. A method of preparing a composite material according to claim 1, wherein: in the step 4), the temperature of the hydrothermal synthesis is 160-200 ℃, and the reaction time is 6-24 h; the rotation speed of the centrifugal separation is 4000-.
8. A method of preparing a composite material according to claim 7, wherein: the temperature of the hydrothermal synthesis is 180 ℃, and the reaction time is 12 h.
9. A method of preparing a composite material according to claim 7, wherein: the rotation speed of the centrifugal separation is 6000rpm/min, and the time is 10 min.
10. A method of preparing a composite material according to claim 1, wherein: in step 5), the thickness of the coated film is 25-200 μm.
11. A method of preparing a composite material according to claim 10, wherein: the thickness of the coated film was 100 μm.
12. A method of preparing a composite material according to claim 1, wherein: in the step 5), the two-step drying method comprises the following steps: drying at 80 deg.C for 3-5h in vacuum environment, and then at 110 deg.C for 1-3 h; the annealing conditions are as follows: temperature rise rate: 10 ℃/min, preserving the heat for 1-3h in the nitrogen atmosphere at the temperature of 350-600 ℃, and then slowly cooling to the room temperature along with the furnace.
13. A preparation method of a methanol gas sensor is characterized by comprising the following steps: the method comprises the following steps: the deposition of Au electrode on the surface of the composite material of claim 1 is carried out by using standard photoetching technology and metal deposition technology.
14. The method of claim 13, wherein: the thickness of the Au electrode is 200nm, and the line width is less than or equal to 0.5 mu m.
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| 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 |
| 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 |
| CN111272825B (en) * | 2020-03-06 | 2022-12-23 | 电子科技大学中山学院 | Metal oxide gas sensor based on surface plasmon enhancement |
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