CN111721813A - Based on tubulose SnO2Array acetone gas sensor and preparation method thereof - Google Patents
Based on tubulose SnO2Array acetone gas sensor and preparation method thereof Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention belongs to the technical field of semiconductor oxide gas sensors, and discloses a gas sensor based on tubular SnO2An array acetone gas sensor and a preparation method thereof, tubular SnO with mesopores by utilizing a template in-situ sacrificial method2A material; by utilizing the unique hollow structure of the tubular array and the high orientation of the one-dimensional array, the CH pair of the sensor is effectively improved3COCH3The sensitivity characteristics of (a). The sensor structure adopted by the invention is Al with 2 annular gold electrodes2O3Insulating ceramic tube, direct growth on electrode and Al2O3Semiconductor sensitive material on surface of insulating ceramic tube and Al-penetrating material2O3The nickel alloy heating coil of the insulating ceramic tube. Compared with the conventional coating process, the device has the advantages of simple process, low cost, and good adhesionSimple process and small volume, thereby detecting CH in environment3COCH3Has wide application in content and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of semiconductor oxide gas sensors, and particularly relates to a gas sensor based on tubular SnO2An acetone gas sensor array and a preparation method thereof.
Background
At present, acetone is widely used as a general purpose reagent in laboratories and industry, once the concentration is higher than 450mg/m3Sometimes, damage to the respiratory tract and nervous system may occur due to their volatile nature. In order to ensure the safety of working and living environments, it is necessary to monitor the concentration of acetone by a rapid and convenient method. In addition, acetone is a respiratory feature of human type I diabetes. By analyzing the acetone concentration in the expired breath of diabetic patients, it was found that the exhaled acetone level exceeded 1.8ppm, whereas the exhaled acetone level of healthy people was 0.35-0.85 ppm. Therefore, it provides a valuable reference for early diagnosis of diabetes and can help patients to get timely treatment. Therefore, the development of acetone sensors with high sensitivity and high selectivity has attracted great attention in recent years.
Tin dioxide (SnO)2) Is a well-known n-type semiconductor gas sensing material due to its wide band gap (E)g3.6eV) and good chemical stability is considered to be the most promising candidate for acetone monitoring. In general, the performance of gas sensors is affected by the microstructure and topography. Hitherto, SnO having various structures have been successfully developed2The gas sensitive material comprises one-dimensional nano fibers, two-dimensional nano sheets and a 3D layered flower-shaped nano structure. Wherein, one-dimensional SnO2Materials are considered to be one of the most superior nanostructures due to their high aspect ratio and ultra-high specific surface area. One-dimensional SnO2Nanotubes have many advantages such as a larger surface area to volume ratio for gas adsorption and desorption, and a better electron transport path. Notably, nanotubes are typically synthesized by templated methods, requiring a secondary acid or baseThe template can be removed by etching, the etching degree is difficult to control, and the method is time-consuming and not environment-friendly. Thus, SnO is synthesized directly on alumina ceramic tubes in a simplified manner2Nanotube arrays remain a challenge to overcome the above-described deficiencies in gas sensing applications.
Through the above analysis, the problems and defects of the prior art are as follows: (1) the manufacturing process of the conventional gas sensor is complicated. In conventional slurry coating manufacturing processes, two steps are typically involved, including preparing the materials and coating them on the alumina ceramic electrode. And during the coating process, the inherent nanostructure of the material may be destroyed. And the sensitive material is directly grown on the alumina ceramic tube, so that the defects of the traditional slurry coating manufacturing process are overcome. And the ordered one-dimensional array formed in situ has excellent sensing performance, and can enhance the transmission of electrons and the diffusion of gas, but the prior art does not utilize the characteristic, so that the sensing performance is poor.
(2) Most of the one-dimensional tubular materials prepared by using the template need to carry out post-treatment on the template, and the template is commonly used
The difficulty in solving the above problems and defects is:
in the present invention, SnO2The formation of a one-dimensional array requires two conditions: (1) presetting a ZnO seed layer with reasonable thickness on the ceramic tube substrate; (2) SnO2The tube formation and in-situ etching of the ZnO template require reasonable solvent concentrations and precise control of reaction times.
The significance of solving the problems and the defects is as follows:
the invention improves the defects of the prior art, on one hand, the sensor with in-situ growth overcomes the complex preparation process of the traditional preparation process, and greatly improves the production efficiency; on the other hand, the template in the invention is etched in situ in the reaction process, and no post-treatment is needed, so that the risk of using acid and alkali is avoided.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a tubular SnO2An acetone gas sensor array and a preparation method thereof, in particular to an acetone gas sensor arrayBased on tubular SnO2CH of array3COCH3A sensor and a method for manufacturing the same.
The invention is realized by that tubular SnO grown on a substrate in situ2Array acetone gas sensor, consisting of Al with 2 separate annular gold electrodes (4) on the outer surface2O3An insulating ceramic tube (1) passing through Al2O3A nickel-cadmium heating coil (3) inside the insulating ceramic tube (1) and Al directly grown on the heating coil2O3SnO on the outer surface of the insulating ceramic tube (1) and the annular gold electrode (4)2The sensitive material film (2), each annular gold electrode (4) is connected with a group of platinum wires (5); SnO2The sensitive material film (2) is obtained by directly growing on a substrate in situ by utilizing a ZnO template sacrifice method. The present invention utilizes SnO2The tubular array is used as a sensitive material, on one hand, the unique hollow structure has larger specific surface area, and provides more active sites and gas transmission in the material; on the other hand, the high orientation of the one-dimensional array is beneficial to the transmission of electrons in the material, so that the CH of the sensor pair is effectively improved3COCH3The sensitivity characteristics of (a). Meanwhile, compared with the traditional coating process, the device has simple process, does not need a coating step, has small volume, and thus detects CH in the environment3COCH3Has wide application in content and is suitable for large-scale production.
Another object of the present invention is to provide a tubular SnO2CH of array3COCH3A method of making a sensor, comprising: SnO2The sensitive material film is obtained by directly growing on a substrate in situ by utilizing a ZnO template sacrifice method.
Further, the preparation steps of the ZnO nanorod array template are as follows:
(1) firstly, commercially available Al with 2 annular gold electrodes on the outer surface2O3The ceramic tube is alternately cleaned by ethanol and acetone and then dried at 60 ℃, and the length of the ceramic chamber is 4-4.5 mm, the outer diameter is 1.2-1.5 mm, and the inner diameter is 0.8-1.0 mm.
(2) 0.3g of zinc acetate was dissolved in 50ml of methanol to obtain a sol solution. Then, the clear liquid in the step (1) is mixedWashed Al2O3The ceramic tube was immersed in the above solution for 30 minutes and annealed at 350 ℃ for 30 minutes to form a ZnO seed layer.
(3) The growth solution was obtained by mixing 0.03M zinc nitrate and 0.03M hexamethylenetetramine solution. Then, the stock solution and the ceramic tube in the step (2) were transferred to a stainless autoclave lined with Teflon, and subjected to hydrothermal reaction at 90 ℃.
(4) Naturally cooling to room temperature, and taking out Al from the solution2O3The tube was ceramic and repeatedly washed with deionized water and ethanol and then dried at 80 ℃ for 6 h.
Further, tubular SnO2CH of array3COCH3The preparation method of the sensor comprises the following steps:
(1) 0.4g of sodium stannate was added to 60ml of a water/ethanol (40 vol% water) mixed solvent. 0.28M urea was added and the suspension was then transferred to a Teflon lined 100ml stainless steel autoclave.
(2) Al with ZnO nano-rod array2O3The tube was suspended above the bottom of the autoclave and heated at 170 ℃ for 60 minutes. Finally, the Al is rinsed with deionized water2O3The tube was ceramic and dried in air.
(3) Passing a nickel-cadmium heating coil with a resistance value of 30-40 omega through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element, so that the tubular SnO is obtained2CH of array3COCH3A sensor.
TABLE 1 comparison of gas-sensitive Properties of nickel cobaltate gas-sensitive sensors
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention relates to tubular SnO with mesopores by utilizing a template in-situ sacrificial method2A material. Height using tubular array unique hollow structure and one-dimensional arrayDegree orientation, effectively improves the CH of the sensor pair3COCH3The sensitivity characteristics of (a). In addition, the sensor structure adopted by the invention is Al with 2 annular gold electrodes2O3Insulating ceramic tube, direct growth on electrode and Al2O3Semiconductor sensitive material on surface of insulating ceramic tube and Al-penetrating material2O3 nickel alloy heating coil for insulating ceramic tube. Compared with the traditional coating process, the device has simple process and small volume, thereby detecting CH in the environment3COCH3Has wide application in content and is suitable for large-scale production.
Compared with the prior art, the invention has the following advantages that:
the invention utilizes a template self-sacrifice method to prepare SnO2The nanotube does not need to be subjected to post-treatment on the template by acid or alkali, and has the characteristics of simple preparation and environmental friendliness;
SnO prepared by the invention2The nano tube has a unique hollow structure, and the specific surface area of the material is effectively improved.
Tubular SnO prepared by the invention2Array acetone gas sensing pair CH3COCH3Has high sensitivity in detecting CH3COCH3Has wide application prospect in the aspect of content.
The sensitive material of the sensor directly grows on the ceramic tube substrate in situ, a coating process is not needed, and the process is simple.
Technical effect or experimental effect of comparison.
The synthesis mode of the gas-sensitive material is a two-step hydrothermal method, and the gas-sensitive material is simple to operate and easy to control. The medicines used in the experimental process of the gas-sensitive material are all common chemical medicines, and the cost is low. The invention synthesizes SnO2Nanotube arrays in contrast to SnO using conventional coating processes2The sensitivity of the nanotube material to acetone gas is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is a tubular SnO base material provided by the embodiment of the invention2A flow chart of a preparation method of the array acetone gas sensor.
FIG. 2 is a tubular SnO provided by embodiments of the present invention2Scanning electron micrograph of array material, wherein the magnification of the inset is 100000 times; SnO can be seen in the figure2The nanotube array has high orientation, and a unique hollow structure can be seen from the insets.
FIG. 3 is a tubular SnO provided by embodiments of the present invention2High transmission electron micrograph of array material; SnO can be seen in the figure2The wall thickness of the nanotubes is about 30 nm.
FIG. 4 is a tubular SnO provided by embodiments of the present invention2An X-ray diffraction pattern of the array material; SnO in the figure2Of materials in SnO2The standard peak (PDF-625) corresponds exactly.
FIG. 5 is a tubular SnO provided by embodiments of the present invention2The structural schematic diagram of the array acetone gas sensor; the device in the figure is made of Al2O3The device comprises an insulating ceramic tube 1, a semiconductor sensitive material 2 grown in situ, a nickel-cadmium heating coil 3, an annular gold electrode 4 and a platinum wire 5.
FIG. 6 shows a sensor pair of 100ppm CH in an embodiment provided by an embodiment of the present invention3COCH3The response versus temperature curve of (a); when the device is in CH3COCH3The optimum operating temperature for the examples was 325 ℃ at a gas concentration of 100ppm, when the device was paired with 100ppm CH3COCH3The sensitivity of (3) was 20.2. Wherein, the sensitivity is the resistance value R of the sensor in the gas to be measuredgAnd resistance value R in airaThe ratio of (a) to (b) is expressed as: r ═ Sg/Ra。
FIG. 7 shows the optimum operating temperature of the sensor for CH concentrations in the comparative examples and examples3COCH3Sensitivity contrast plot of (1).
FIG. 8 is a graph showing the results of comparative examples and examples for various concentrations (5ppm to 100ppm) of CH3COCH3Dynamic response recovery curve of gas.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a tubular SnO2The invention relates to an array acetone gas sensor and a preparation method thereof, which are described in detail in the following with reference to the accompanying drawings.
Comparative example 1
In non-substrate SnO2The nano tube sensitive material is used for manufacturing the indirectly heated acetone sensor, and the specific manufacturing process is as follows:
(1) 0.03M zinc nitrate and 0.03M hexamethylenetetramine solution were mixed, and then the stock solution was transferred to a Teflon-lined stainless steel autoclave, subjected to hydrothermal reaction at 90 ℃ and collected.
(2) 0.4g of sodium stannate was added to 60ml of a water/ethanol (40 vol% water) mixed solvent. 0.28M urea was added and the suspension was then transferred to a Teflon lined 100ml stainless steel autoclave and 0.3g of the product from step (1) was added to the mixed solution and heated at 170 ℃ for 60 minutes. Finally, the product was collected by centrifugation and dried in air.
(3) And (3) taking a small amount of prepared sensitive material powder, dripping deionized water according to the mass ratio of 5:1, and grinding into pasty slurry. Then a small amount of slurry is taken by a brush to be evenly coated on the Al of a commercial Al electrode with 2 separated annular gold electrodes on the outer surface2O3A sensitive material film with the thickness of 30 microns is formed on the surface of an insulating ceramic tube, the length of the ceramic tube is 4mm, the outer diameter of the ceramic tube is 1.2mm, the inner diameter of the ceramic tube is 0.8mm, and the sensitive material completely covers the annular gold electrode.
(4) Baking under infrared lamp for 20 min, drying the sensitive material, and adding Al2O3The ceramic tube is roasted for 2 hours at 350 ℃; passing a nickel-cadmium heating coil with a resistance value of 30-40 omega through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element, so that the SnO based on the coating process is obtained2CH of nanotube3COCH3Sensor with a sensor element
Example 1
The present invention utilizes SnO2The tubular array is used as a sensitive material, on one hand, the unique hollow structure has larger specific surface area, and provides more active sites and gas transmission in the material; on the other hand, the high orientation of the one-dimensional array is beneficial to the transmission of electrons in the material, so that the CH of the sensor pair is effectively improved3COCH3The sensitivity characteristics of (a). Meanwhile, compared with the traditional coating process, the device has simple process, does not need a coating step, has small volume, and thus detects CH in the environment3COCH3Has wide application in content and is suitable for large-scale production.
The invention provides tubular SnO grown in situ on a substrate2Array acetone gas sensor, consisting of Al with 2 separate annular gold electrodes (4) on the outer surface2O3An insulating ceramic tube (1) passing through Al2O3A nickel-cadmium heating coil (3) inside the insulating ceramic tube (1) and Al directly grown on the heating coil2O3SnO on the outer surface of the insulating ceramic tube (1) and the annular gold electrode (4)2The sensitive material film (2), each annular gold electrode (4) is connected with a group of platinum wires (5); SnO2The sensitive material film (2) is obtained by directly growing on a substrate in situ by utilizing a ZnO template sacrifice method.
The preparation method of the ZnO nanorod array template comprises the following steps: (1) firstly, commercially available Al with 2 annular gold electrodes on the outer surface2O3The ceramic tube is alternately cleaned by ethanol and acetone and then dried at 60 ℃, and the length of the ceramic chamber is 4-4.5 mm, the outer diameter is 1.2-1.5 mm, and the inner diameter is 0.8-1.0 mm.
(2) 0.3g of zinc acetate was dissolved in 50ml of methanol to obtain a sol solution. Then, the user can use the device to perform the operation,al cleaned in the step (1)2O3The ceramic tube was immersed in the above solution for 30 minutes and annealed at 350 ℃ for 30 minutes to form a ZnO seed layer.
(3) The growth solution was obtained by mixing 0.03M zinc nitrate and 0.03M hexamethylenetetramine solution. Then, the stock solution and the ceramic tube in the step (2) were transferred to a stainless autoclave lined with Teflon, and subjected to hydrothermal reaction at 90 ℃.
(4) Naturally cooling to room temperature, and taking out Al from the solution2O3The tube was ceramic and repeatedly washed with deionized water and ethanol and then dried at 80 ℃ for 6 h.
As shown in FIG. 1, the tubular SnO of the present invention2CH of array3COCH3The preparation method of the sensor comprises the following steps:
s101, 0.4g of sodium stannate was added to 60ml of a water/ethanol (40 vol% water) mixed solvent. 0.28M urea was added and the suspension was then transferred to a Teflon lined 100ml stainless steel autoclave.
S102, mixing Al with ZnO nano-rod array2O3The tube was suspended above the bottom of the autoclave and heated at 170 ℃ for 60 minutes. Finally, the Al is rinsed with deionized water2O3The tube was ceramic and dried in air.
S103, passing a nickel-cadmium heating coil with a resistance value of 30-40 omega through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element, so that the tubular SnO is obtained2CH of array3COCH3A sensor.
Example 2:
with tubular SnO2The gas sensor is manufactured by using the nanotube array as a sensitive material, and the specific manufacturing process comprises the following steps:
1) the commercially available Al with 2 annular gold electrodes on the outer surface2O3The ceramic tube is alternately cleaned by ethanol and acetone and then dried at 60 ℃, and the length of the ceramic chamber is 4-4.5 mm, the outer diameter is 1.2-1.5 mm, and the inner diameter is 0.8-1.0 mm.
2) 0.3g of BZinc salt was dissolved in 50ml of methanol to obtain a sol solution. Then, the cleaned Al is removed2O3The ceramic tube was immersed in the above solution for 30 minutes and annealed at 350 ℃ for 30 minutes to form a ZnO seed layer.
3) The growth solution was obtained by mixing 0.03M zinc nitrate and 0.03M hexamethylenetetramine solution. The stock solution and the ceramic tube in step 2 were then transferred to a teflon-lined stainless steel autoclave and subjected to hydrothermal reaction at 90 ℃ for 2 hours. Naturally cooling to room temperature, and taking out Al from the solution2O3And (3) a ceramic tube, wherein a ZnO nanorod array grows on the ceramic tube. Repeatedly washing with deionized water and ethanol, and drying at 80 deg.C for 6 hr.
4) 0.4g of sodium stannate was added to 60ml of a water/ethanol (40 vol% water) mixed solvent. 0.28M Urea was added and the suspension was then transferred to a Teflon lined 100ml stainless steel autoclave Al with ZnO nanorod arrays2O3The tube was suspended above the bottom of the autoclave and heated at 170 ℃ for 60 minutes. Finally, the Al is rinsed with deionized water2O3The tube was ceramic and dried in air.
5) And penetrating a nickel-cadmium heating coil with a resistance value of 30-40 omega through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element, so that the tubular SnO is obtained2CH of array3COCH3A sensor.
In the present invention, FIG. 2 is a tubular SnO provided by an embodiment of the present invention2Scanning electron micrograph of array material, wherein the magnification of the inset is 100000 times; SnO can be seen in FIG. 22The nanotube array has high orientation, and a unique hollow structure can be seen from the insets.
FIG. 3 is a tubular SnO provided by embodiments of the present invention2High transmission electron micrograph of array material; SnO can be seen in FIG. 32The wall thickness of the nanotubes is about 30 nm.
FIG. 4 is a tubular SnO provided by embodiments of the present invention2An X-ray diffraction pattern of the array material; SnO in FIG. 42Of materials in SnO2The standard peak (PDF-625) corresponds exactly. The sensitive material is proved to have good crystallinity.
FIG. 5 is a tubular SnO provided by embodiments of the present invention2The structural schematic diagram of the array acetone gas sensor; the device of FIG. 5 is made of Al2O3The device comprises an insulating ceramic tube 1, a semiconductor sensitive material 2 grown in situ, a nickel-cadmium heating coil 3, an annular gold electrode 4 and a platinum wire 5.
FIG. 6 shows a sensor pair of 100ppm CH in an embodiment provided by an embodiment of the present invention3COCH3The response versus temperature curve of (a); in FIG. 6 when the device is in CH3COCH3The optimum operating temperature for the examples was 325 ℃ at a gas concentration of 100ppm, when the device was paired with 100ppm CH3COCH3The sensitivity of (3) was 20.2. Wherein, the sensitivity is the resistance value R of the sensor in the gas to be measuredgAnd resistance value R in airaThe ratio of (a) to (b) is expressed as: r ═ Sg/Ra。
FIG. 7 shows the optimum operating temperature of the sensor for CH concentrations in the comparative examples and examples3COCH3Sensitivity contrast plot of (1). The response of the embodiment to common VOC gas is higher than that of the comparative example, particularly to acetone, and the in-situ growth process is proved to be superior to the traditional coating process, and the prepared gas sensor has higher response and is more suitable for mass production and preparation.
FIG. 8 is a graph showing the results of comparative examples and examples for various concentrations (5ppm to 100ppm) of CH3COCH3Dynamic response recovery curve of gas. It can be seen from the figure that the response of the example to the target gas is higher than that of the comparative example under all concentrations, and the example can be used in a larger concentration range and is more suitable for practical application scenarios.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. Tubular SnO growing on substrate in situ2The preparation method of the array acetone gas sensor is characterized in that the tubular SnO grown on the substrate in situ2The preparation method of the array acetone gas sensor comprises the following steps:
SnO prepared by ZnO nanorod array template sacrificial method2The sensitive material film is grown on the substrate in situ to prepare tubular SnO grown on the substrate in situ2And (5) array acetone gas sensors.
2. Tubular SnO of claim 1 grown in situ on substrate2The preparation method of the array acetone gas sensor is characterized in that the preparation method of the ZnO nanorod array template comprises the following steps:
(1) al with 2 annular gold electrodes on the outer surface2O3Cleaning the ceramic tube with ethanol and acetone alternately, and drying;
(2) dissolving zinc acetate in methanol to obtain a sol solution; then, Al cleaned in the step (1) is added2O3Immersing the ceramic tube into the solution, and annealing to form a ZnO seed crystal layer;
(3) obtaining a growth solution through a mixed zinc nitrate and hexamethylenetetramine solution; then transferring the stock solution and the ceramic tube in the step (2) into a stainless steel autoclave with a Teflon lining for hydrothermal reaction;
(4) naturally cooling to room temperature, and taking out Al from the solution2O3The tube was repeatedly washed with deionized water and ethanol and then dried.
3. Tubular SnO in situ grown on substrate according to claim 22The preparation method of the array acetone gas sensor is characterized in that in the step (1), the Al is2O3After the ceramic tube is alternately cleaned by ethanol and acetone, the ceramic tube is dried at 60 ℃, the length of a ceramic museum is 4-4.5 mm, the outer diameter is 1.2-1.5 mm, and the inner diameter is 0.8-1.0 mm;
in the step (2), the Al2O3The ceramic tube was immersed in the solution for 30 minutes and annealed at 350 ℃ for 30 minutes;
in the step (3), the stock solution and the ceramic tube are transferred into a stainless steel autoclave with a Teflon lining, and hydrothermal reaction is carried out at 90 ℃;
in the step (4), after naturally cooling to room temperature, taking out Al from the solution2O3The tube was ceramic and repeatedly washed with deionized water and ethanol and then dried at 80 ℃ for 6 h.
4. Tubular SnO of claim 1 grown in situ on substrate2The preparation method of the array acetone gas sensor is characterized in that the tubular SnO grown on the substrate in situ2The preparation method of the array acetone gas sensor further comprises the following steps:
(1) adding sodium stannate into a water/ethanol mixed solvent; urea is added and then the suspension is transferred to a teflon lined stainless steel autoclave;
(2) al with ZnO nano-rod array2O3The tube was suspended above the bottom of the autoclave and heated at 170 ℃ for 60 minutes; finally, the Al is rinsed with deionized water2O3Ceramic tubes and drying in air;
(3) passing a nickel-cadmium heating coil with a resistance value of 30-40 omega through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the components are carried out according to a general indirectly heated gas sensitive elementWelding and packaging to obtain a tubular SnO base2CH of array3COCH3A sensor.
5. Tubular SnO of claim 1 grown in situ on substrate2The preparation method of the array acetone gas sensor is characterized in that the tubular SnO grown on the substrate in situ2The preparation method of the array acetone gas sensor further comprises the following steps:
1) al with 2 annular gold electrodes on the outer surface2O3Cleaning the ceramic tube with ethanol and acetone alternately, and drying at 60 ℃;
2) and zinc acetate was dissolved in 50ml of methanol to obtain a sol solution. Then, the cleaned Al is removed2O3Immersing the ceramic tube into the solution for 30 minutes, and annealing at 350 ℃ for 30 minutes to form a ZnO seed crystal layer;
3) obtaining a growth solution through a mixed zinc nitrate and hexamethylenetetramine solution; then transferring the stock solution and the ceramic tube in the step 2) into a stainless steel autoclave with a Teflon lining, and carrying out hydrothermal reaction for 2 hours at 90 ℃; naturally cooling to room temperature, and taking out Al from the solution2O3A ZnO nanorod array is grown on the ceramic tube; repeatedly washing with deionized water and ethanol, and drying at 80 deg.C for 6 hr;
4) adding sodium stannate into a water/ethanol mixed solvent; urea is added and then the suspension is transferred to a teflon lined stainless steel autoclave; al with ZnO nano-rod array2O3The tube was suspended above the bottom of the autoclave and heated at 170 ℃ for 60 minutes; finally, the Al is rinsed with deionized water2O3Ceramic tubes and drying in air;
5) passing a nickel-cadmium heating coil through Al2O3The interior of the ceramic tube is used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element to obtain tubular SnO growing on the substrate in situ2Array acetone gas sensor base.
6. An application rightTubular SnO prepared by any one of the preparation methods and growing on a substrate in situ2And (5) array acetone gas sensors.
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