CN113447557A - Based on hollow six mango star Co3O4Methanol sensor made of material, preparation method and application - Google Patents
Based on hollow six mango star Co3O4Methanol sensor made of material, preparation method and application Download PDFInfo
- Publication number
- CN113447557A CN113447557A CN202110585032.2A CN202110585032A CN113447557A CN 113447557 A CN113447557 A CN 113447557A CN 202110585032 A CN202110585032 A CN 202110585032A CN 113447557 A CN113447557 A CN 113447557A
- Authority
- CN
- China
- Prior art keywords
- hollow
- gas
- sensor
- ceramic tube
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4162—Systems investigating the composition of gases, by the influence exerted on ionic conductivity in a liquid
Abstract
The invention belongs to the technical field of gas sensor preparation, and discloses a hollow hexagram Co-based sensor3O4Methanol sensor made of material, preparation method and application thereof, and based on hollow hexa-mango star Co3O4A methanol sensor of material comprising: a platinum lead, a gold electrode, a ceramic tube, a gas-sensitive material layer and a nichrome heating coil; the ceramic tube is an alumina ceramic tube; the alumina ceramic tube is provided with 2 Au electrodes and 4 Pt leads; co3O4The gas-sensitive material layer uniformly covers the outer surface of the alumina ceramic tube; the nichrome heating coil penetrates through the inner side of the ceramic tube and is used for controlling the working temperature of the gas sensor. The invention successfully synthesizes Co by a one-step hydrothermal method3O4A gas sensitive material. The synthetic method is simple and the cost is low; the invention takes ammonium fluoride as a structure directing agent, realizes the construction of a hollow three-dimensional structure, and has simple synthesis method and low cost.
Description
Technical Field
The invention belongs to the technical field of gas sensor preparation, and particularly relates to a hollow hexagram Co-based sensor3O4A methanol sensor made of the material, a preparation method and application.
Background
At present: methanol (methanol, CH)3OH) which is also called hydroxymethane, is saturated monohydric alcohol with the simplest structure, is a representative volatile organic compound, is colorless and transparent, and is completely mutually soluble with water. The method is widely used for organic synthesis raw materials, organic solvents, cleaning agents and the like in factories and laboratories. Methanol is highly toxic. Industrial alcohol contains about 4% of methanol, and if lawless persons take it as edible alcohol to make fake wine, it will produce methanol poisoning after drinking. The lethal dose of methanol is about 70 ml. The toxicity of methanol has the greatest impact on the nervous system and the blood system of the human body, a toxic reaction is generated when the methanol is taken through the digestive tract, the respiratory tract or the skin, and methanol vapor can damage the respiratory mucosa and the vision of the human body. In methanol production plants, the China department concerned stipulates that the concentration of air methanol is limited to 50mg/m PC-stel3And the PC-TWA is 25mg/m3, a gas mask is required to be worn in site work with methanol gas, and the factory wastewater can be discharged after being treated, so that the content of the methanol is allowed to be less than 200 mg/L. In view of the wide range of methanol presence and serious hazards in life, it is highly desirable to develop a high performance gas sensor to detect the effects of methanol concentration on human health.
Among various gas detection technologies, a gas sensor based on a semiconductor oxide has become a leading-edge hotspot of research due to the advantages of small volume, high reliability, rapid response, easy integration and the like. Cobalt tetraoxide (Co) with spinel crystal structure in sensing material based on metal oxide semiconductor material3O4) Especially for treating acute hepatitisIts excellent catalytic activity and polyvalent property (Co)2+/Co3+) Making it a competitive gas sensitive material. At the same time, Co3O4As a typical p-type sensitive material, the material has the unique advantages of low working temperature, high selectivity, good moisture resistance, high thermal stability and the like, and is also favorable for realizing a gas sensor with high gas-sensitive performance. However, the low response inherent in p-type sensing materials limits their applications. Therefore, Co is further improved3O4Gas sensing performance of the gas sensor. Since the processes of adsorption, desorption and surface reaction of gas depend to a large extent on the microstructure of the material, controlling the synthetic microstructure is a key factor in improving gas sensitivity. The three-dimensional hierarchical nano structure is particularly prominent, and the unique hierarchical structure can effectively inhibit the aggregation of nano particles and increase the exposure of active sites. Meanwhile, the construction of hollow structures can further improve the gas-sensitive performance because their high specific surface area facilitates electron transfer and surface reaction of chemical reactants (such as gas or ions). However, the synthesis process of the hollow three-dimensional structure of the reported structure is complex, is not beneficial to wide application and needs to be improved.
Through the above analysis, the problems and defects of the prior art are as follows: existing based on Co3O4The sensitivity of the sensor is low, and effective detection of gas is difficult to realize; and the synthesis process of the hollow three-dimensional structure material is complex.
The difficulty in solving the above problems and defects is: how to utilize the effective structure directing agent and realize the construction of the flower-shaped structure by a simple process; the construction of the hollow three-dimensional structure is beneficial to increasing the specific surface area of the product, improving the diffusion speed of gas molecules, providing a high-efficiency reaction field for the adsorption oxidation reaction of gas, and further realizing the improvement of the gas-sensitive performance. However, the synthesis process of the hollow three-dimensional structure of the reported structure is complex, is not beneficial to wide application and needs to be improved.
The significance of solving the problems and the defects is as follows: construction of three-dimensional hierarchical Co3O4The material is beneficial to preparing a high-performance methanol gas sensor and effectively applying the sensor to daily methanol gasAnd (6) detecting.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hollow hexagram Co-based material3O4A methanol sensor made of the material, a preparation method and application.
The invention is realized by the following steps that3O4Methanol sensor of material, the methanol sensor is based on hollow hexammine Co3O4A methanol sensor of material comprising: a platinum lead, a gold electrode, a ceramic tube, a gas-sensitive material layer and a nichrome heating coil;
the ceramic tube is an alumina ceramic tube; the aluminum oxide ceramic tube is provided with 2 Au electrodes and 4 Pt leads;
the Co3O4The gas-sensitive material layer uniformly covers the outer surface of the alumina ceramic tube;
the nickel-chromium alloy heating coil penetrates through the inner side of the ceramic tube and is used for controlling the working temperature of the gas sensor.
Further, the Co3O4The gas-sensitive material is prepared by taking 2-10 g of cobalt source and 8-50 g of structure directing agent as precursors;
the cobalt source is cobalt nitrate; the structure directing agent is ammonium fluoride.
The invention also aims to provide a hollow hexammine Co-based alloy3O4Preparation method of methanol sensor based on material, wherein hollow hexammine Co is adopted3O4The preparation method of the methanol sensor of the material comprises the following steps:
by mixing hollow hexagnan Co3O4The gas-sensitive material is uniformly coated on the outer surface of the ceramic tube and assembled according to the indirectly heated device process to obtain the hollow six-elongated-star Co3O4A methanol gas sensor.
Further, the hollow hexammine-based Co3O4The preparation method of the methanol sensor comprises the following steps:
step one, cobalt nitrate and ammonium fluoride are used as precursors, a mixed solution of ethanol and water is used as a solvent,one-step hydrothermal synthesis of hollow hexamicin Co3O4A gas sensitive material;
step two, cleaning the alumina ceramic tube by using ethanol, and drying; the prepared hollow hexagram-shaped Co3O4Grinding and mixing the gas-sensitive material and deionized water to form slurry, uniformly coating the slurry on the outer surface of the ceramic tube, and drying;
welding the ceramic tube coated with the gas-sensitive material on a hexagonal base through pins to obtain a hollow hexagram-shaped Co3O4A gas sensor.
Further, in the step one, the hollow hexammine Co is synthesized by taking cobalt nitrate and ammonium fluoride as precursors and taking a mixed solution of ethanol and water as a solvent through a one-step hydrothermal method3O4The gas sensitive material includes:
firstly, fully stirring cobalt nitrate and ammonium fluoride at room temperature, and dissolving the cobalt nitrate and the ammonium fluoride in a mixed solvent of ethanol and water to obtain a uniformly mixed solution;
secondly, transferring the obtained mixed uniform solution into a high-pressure reaction kettle with the capacity of 50ml to perform hydrothermal reaction, and after the reaction is finished, alternately centrifuging the reaction precipitate by using ethanol and deionized water;
finally, drying the centrifugal product at 60 ℃ for 24h, and annealing the dried product at 500 ℃ to obtain hollow hexammine Co3O4A gas sensitive material.
Further, the step of fully stirring the cobalt nitrate and the ammonium fluoride at room temperature comprises the following steps: the stirring time was 25min and the stirring speed was 500-.
Further, the hydrothermal reaction comprises: reacting for 6-25 h at 70-2000 ℃.
Further, the alternating centrifugation comprises: the time of each centrifugation is 8min, and the centrifugation speed is 400-1000 rpm.
Further, in the second step, the cleaning the alumina ceramic tube with ethanol includes: and simultaneously putting 3-5 ceramic tubes into a 100ml beaker, and respectively carrying out ultrasonic cleaning for six times by using ethanol and acetone alternately, wherein the ultrasonic time is 10min each time.
Further, the hollow six preparedAsterisk shaped Co3O4The grinding and mixing of the gas sensitive material and the deionized water comprises the following steps:
0.02g of hollow hexagram-shaped Co3O4The gas sensitive material is put in a mortar, and then a dropper is used to gradually drop 2ml of deionized water, and the mixture is ground for 15s and mixed to form uniform slurry.
The invention also aims to provide a gas sensor which adopts the hollow hexammine Co-based gas sensor3O4A methanol sensor of the material.
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention successfully synthesizes Co by a one-step hydrothermal method3O4A gas sensitive material. The synthetic method is simple and the cost is low; the invention takes ammonium fluoride as a structure directing agent, realizes the construction of a hollow three-dimensional structure, and has simple synthesis method and low cost.
The invention improves Co through the construction of a hollow three-dimensional structure3O4The performance of the methanol-based gas sensor shows that the test result shows that the hollow hexagram Co prepared by the method of the invention3O4The sensitivity of the sensor made of the material to 100ppm of methanol gas at the optimal working temperature of 150 ℃ is 4.5, the sensor has excellent sensing characteristics to the methanol gas, and the effective detection to the methanol at low temperature can be realized. And the synthesis process is simple.
Drawings
FIG. 1 is a hollow hexagram Co-based design provided by an embodiment of the present invention3O4A flow chart of a preparation method of the material methanol sensor.
FIG. 2 is a hollow hexagram Co provided by an embodiment of the present invention3O4Scanning electron micrograph of material.
FIG. 3 is a hollow hexagram Co provided by an embodiment of the present invention3O4High transmission electron micrograph of material.
FIG. 4 is a hollow hexagram-shaped Co3O4X-ray diffraction pattern of the material.
FIG. 5 shows a hollow hexagram Co provided by an embodiment of the present invention3O4The response of the gas sensor to 100ppm methanol is plotted as a function of temperature.
FIG. 6 is a hollow hexagram Co-based design provided by an embodiment of the present invention3O4The device structure of the methanol sensor made of the material is shown schematically.
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 hollow hexagram Co-based material3O4The invention discloses a methanol sensor made of a material, a preparation method and application thereof, and is described in detail below with reference to the accompanying drawings.
The embodiment of the invention provides a hollow hexagram Co-based material3O4A methanol sensor of material comprising: a platinum lead, a gold electrode, a ceramic tube, a gas-sensitive material layer and a nichrome heating coil;
the ceramic tube is an alumina ceramic tube; the alumina ceramic tube is provided with 2 Au electrodes and 4 Pt leads;
Co3O4the gas-sensitive material layer uniformly covers the outer surface of the alumina ceramic tube;
the nichrome heating coil penetrates through the inner side of the ceramic tube and is used for controlling the working temperature of the gas sensor.
Co provided by the embodiment of the invention3O4The gas-sensitive material is prepared by using 2-10 g of cobalt nitrate and 8-50 g of ammonium fluoride as precursors.
The embodiment of the invention provides a hollow hexagram Co-based material3O4The preparation method of the methanol sensor of the material comprises the following steps:
by mixing hollow hexagnan Co3O4The gas-sensitive material is uniformly coated on the outer surface of the ceramic tube and assembled according to the indirectly heated device process to obtain the hollow six-elongated-star Co3O4A methanol gas sensor.
As shown in figure 1, the hollow hexammine-based Co provided by the embodiment of the invention3O4The methanol sensor of the material, the preparation method and the application comprise the following steps:
s101, synthesizing hollow hexamicin Co by using cobalt nitrate and ammonium fluoride as precursors and using a mixed solution of ethanol and water as a solvent through a one-step hydrothermal method3O4A gas sensitive material;
s102, cleaning the alumina ceramic tube by using ethanol, and drying; the prepared hollow hexagram-shaped Co3O4Grinding and mixing the gas-sensitive material and deionized water to form slurry, uniformly coating the slurry on the outer surface of the ceramic tube, and drying;
s103, welding the ceramic tube coated with the gas-sensitive material on a hexagonal base through pins to obtain a hollow hexagram-shaped Co3O4A gas sensor.
The hollow hexamicin Co is synthesized by a one-step hydrothermal method by taking cobalt nitrate and ammonium fluoride as precursors and a mixed solution of ethanol and water as a solvent3O4The gas sensitive material includes:
firstly, stirring cobalt nitrate and ammonium fluoride at room temperature at 500-1200rpm for 25min, and dissolving the cobalt nitrate and the ammonium fluoride in a mixed solvent of ethanol and water to obtain a uniformly mixed solution;
secondly, transferring the obtained mixed uniform solution into a high-pressure reaction kettle with the capacity of 50ml, reacting for 6-25 h at 70-2000 ℃, and after the reaction is finished, alternately centrifuging the reaction precipitate by using ethanol and deionized water;
finally, drying the centrifugal product at 60 ℃ for 24h, and annealing the dried product at 500 ℃ to obtain hollow hexammine Co3O4A gas sensitive material.
The alternate centrifugation provided by the embodiment of the invention comprises the following steps: the time of each centrifugation is 8min, and the centrifugation speed is 400-1000 rpm.
The embodiment of the invention provides a method for cleaning an alumina ceramic tube by using ethanol, which comprises the following steps: and simultaneously putting 3-5 ceramic tubes into a 100ml beaker, and respectively carrying out ultrasonic cleaning for six times by using ethanol and acetone alternately, wherein the ultrasonic time is 10min each time.
The embodiment of the invention provides hollow hexagram Co to be prepared3O4The grinding and mixing of the gas sensitive material and the deionized water comprises the following steps:
0.02g of hollow hexagram-shaped Co3O4The gas sensitive material is put in a mortar, and then a dropper is used to gradually drop 2ml of deionized water, and the mixture is ground for 15s and mixed to form uniform slurry.
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1:
the invention provides a method for preparing Co based on okra3O4The preparation method of the acetone sensor comprises the following steps:
(1) the hollow hexammine Co is prepared by a one-step hydrothermal method by taking cobalt nitrate as a metal salt, ethanol/water mixed solution as a solvent and ammonium fluoride as a surfactant3O4Material
(2) The synthesis process based on the hollow six-mango star Co is finished according to the indirectly heated device synthesis process3O4And (4) preparing a methanol sensor.
The hollow hexagram Co3O4The content of chemical reagents in the preparation process of the gas sensitive material is respectively 2-10 g of cobalt nitrate; 8-50 g of ammonium fluoride; 5-60 mL of ethanol/water mixed solution;
the invention also aims to provide a hollow hexammia Co3O4The specific preparation method of the gas sensitive material comprises the following steps:
(1) fully stirring a certain amount of cobalt nitrate and ammonium fluoride at room temperature, and dissolving the cobalt nitrate and the ammonium fluoride in a mixed solvent of ethanol and water to form a uniform solution;
(2) transferring the uniform solution into a high-pressure reaction kettle with the capacity of 50ml, sealing and screwing, and putting into a constant-temperature oven for hydrothermal reaction;
(3) after the hydrothermal reaction is finished, alternately centrifuging the reaction precipitate by using ethanol and deionized water at the centrifugation speed of 500-900 rpm;
(4) the centrifuged product was dried in an oven at 60 ℃ overnight;
(5) annealing the dried product at 500 ℃ to obtain hollow hexammine Co3O4A gas sensitive material.
The invention completes the process based on the hollow six-mango star Co according to the indirectly heated device process3O4The preparation method of the sensor specifically comprises the following steps:
(1) hollow six mango star Co3O4Grinding the material powder and deionized water to form uniform slurry;
(2) and (3) taking a small amount of slurry material, and uniformly coating the slurry material on the outer surface of the ceramic tube to form a gas sensing layer with the thickness of 3-30 microns.
(3) Placing the coated ceramic tube at room temperature for drying, and then placing the ceramic tube into a muffle furnace for calcining at 350 ℃ for 30 min;
(4) passing a nickel-chromium heating coil through the inside of the calcined ceramic tube to control the operating temperature;
(5) welding and fixing the ceramic tube on a hexagonal base to finish the process based on the hollow six-mango star Co3O4Preparing a sensor;
the grinding and mixing mode of the materials and the deionized water is as follows: firstly, hollow hexagram Co3O4And putting the powder into a mortar, then adding deionized water dropwise, and grinding for 10-30 s.
The method successfully prepares the hollow hexammine-based Co3A methanol sensor of O material. The gas sensor has excellent sensing characteristics on methanol gas, the sensitivity is 4.5, the optimal working temperature is 150 ℃, and the effective detection on methanol at low temperature can be realized. And the synthesis process is simple.
Example 2:
the invention is based on okra-like Co3O4The preparation method of the acetone sensor comprises the following steps:
fully stirring a certain amount of cobalt nitrate and ammonium fluoride at room temperature, and dissolving the cobalt nitrate and the ammonium fluoride in a mixed solvent of ethanol and water to form a uniform solution; transferring the uniform solution into a high-pressure reaction kettle with the capacity of 50ml, sealing and screwing, and putting into a constant-temperature oven for hydrothermal reaction; after the hydrothermal reaction is finished, alternately centrifuging the reaction precipitate by using ethanol and deionized water at the centrifugation speed of 500-900 rpm; will be provided withThe centrifuged product was dried in an oven at 60 ℃ overnight; annealing the dried product at 500 ℃ to obtain hollow hexammine Co3O4A gas sensitive material.
Hollow six mango star Co3O4Grinding the material powder and deionized water to form uniform slurry; and (3) taking a small amount of slurry material, and uniformly coating the slurry material on the outer surface of the ceramic tube to form a gas sensing layer with the thickness of 3-30 microns. Placing the coated ceramic tube at room temperature for drying, and then placing the ceramic tube into a muffle furnace for calcining at 350 ℃ for 30 min; passing a nickel-chromium heating coil through the inside of the calcined ceramic tube to control the operating temperature; welding and fixing the ceramic tube on a hexagonal base to finish the process based on the hollow six-mango star Co3O4And (4) preparing the sensor.
The technical effects of the present invention will be described in detail with reference to specific experiments.
The invention prepares okra-shaped Co3O4Material parameter information: the content of each chemical reagent in the preparation process is 2-10 g of cobalt nitrate; 8-50 g of ammonium fluoride; 5-60 mL of ethanol/water mixed solution.
Given preparation based on okra-like Co3O4Acetone sensor parameter information of material: okra-like Co3O4And mixing the material powder with deionized water, and grinding for 10-30 s.
Through the experimental data, the hollow hexagram Co is completed3O4A material.
The hollow six mango star Co-based test is completed through the experimental data3O4The prepared methanol gas sensor can realize effective detection of methanol gas, the sensitivity is 4.5, and the optimal working temperature is 150 ℃.
FIG. 2 shows that the prepared hollow hexagram-shaped Co3O4The material has a distinct hollow three-dimensional structure. Fig. 3 hollow hexagram Co3O4High transmission electron micrograph of the material further confirmed the successful formation of hollow three-dimensional structures.
FIG. 4 is a hollow hexagram-shaped Co3O4The X-ray diffraction pattern of the material shows that the main body of the prepared gas-sensitive material is Co3O4The corresponding standard card is PDF # 76-1802.
FIG. 5 shows a hollow hexagram Co provided by an embodiment of the present invention3O4The response of the gas sensor to 100ppm methanol as a function of temperature is seen to be up to 4.5 at 150 deg.C for 100ppm n-butanol.
FIG. 6 shows a hollow hexagram Co-based device according to an embodiment of the present invention3O4The device structure of the methanol sensor made of the material is shown schematically.
The invention is based on hollow hexagram Co3O4The working mechanism of the material methanol sensor is that the resistance value changes when the sensor is in different environments. When the material is placed in air, oxygen molecules absorb electrons and adsorb on the surface of the material, the hole density is increased, and the working resistance is low. When placed in n-butanol, the adsorbed oxygen reacts with methanol molecules to produce CO2、H2O and free electrons, which will return to the conduction band to form electron-hole pairs, the hole density decreases and the working resistance increases.
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 (10)
1. Based on cavity six mango star Co3O4Methanol sensor of material, characterized in that, the methanol sensor is based on hollow hexammine Co3O4A methanol sensor of material comprising: a platinum lead, a gold electrode, a ceramic tube, a gas-sensitive material layer and a nichrome heating coil;
the ceramic tube is an alumina ceramic tube; the aluminum oxide ceramic tube is provided with 2 Au electrodes and 4 Pt leads;
the Co3O4The gas-sensitive material layer uniformly covers the outer surface of the alumina ceramic tube;
the nickel-chromium alloy heating coil penetrates through the inner side of the ceramic tube and is used for controlling the working temperature of the gas sensor.
2. The hollow hexammine Co-based material of claim 13O4Methanol sensor of material, characterized in that said Co3O4The gas-sensitive material is prepared by taking 2-10 g of cobalt source and 8-50 g of structure directing agent as precursors;
the cobalt source is cobalt nitrate; the structure directing agent is ammonium fluoride.
3. A hollow hexammine Co-based alloy as claimed in any one of claims 1-23O4The preparation method of the methanol sensor based on the material is characterized in that the methanol sensor based on the hollow hexammine Co3O4The preparation method of the methanol sensor of the material comprises the following steps:
by mixing hollow hexagnan Co3O4The gas-sensitive material is uniformly coated on the outer surface of the ceramic tube and assembled according to the indirectly heated device process to obtain the hollow six-elongated-star Co3O4A methanol gas sensor.
4. The hollow hexammine Co-based material of claim 33O4The preparation method of the methanol sensor based on the material is characterized in that the methanol sensor based on the hollow hexammine Co3O4The preparation method of the methanol sensor comprises the following steps:
step one, taking cobalt nitrate and ammonium fluoride as precursors, taking a mixed solution of ethanol and water as a solvent, and synthesizing hollow hexamicin Co by a one-step hydrothermal method3O4A gas sensitive material;
step two, cleaning the alumina ceramic tube by using ethanol, and drying; the prepared hollow hexagram-shaped Co3O4Grinding and mixing the gas-sensitive material and deionized water to form slurry, uniformly coating the slurry on the outer surface of the ceramic tube, and drying;
welding the ceramic tube coated with the gas-sensitive material on a hexagonal base through pins to obtain a hollow hexagram-shaped Co3O4A gas sensor.
5. The hollow hexammine Co-based material of claim 43O4The preparation method of the material methanol sensor is characterized in that in the step one, the hollow hexammine Co is synthesized by a one-step hydrothermal method by taking cobalt nitrate and ammonium fluoride as precursors and taking a mixed solution of ethanol and water as a solvent3O4The gas sensitive material includes:
firstly, fully stirring cobalt nitrate and ammonium fluoride at room temperature, and dissolving the cobalt nitrate and the ammonium fluoride in a mixed solvent of ethanol and water to obtain a uniformly mixed solution;
secondly, transferring the obtained mixed uniform solution into a high-pressure reaction kettle with the capacity of 50ml to perform hydrothermal reaction, and after the reaction is finished, alternately centrifuging the reaction precipitate by using ethanol and deionized water;
finally, drying the centrifugal product at 60 ℃ for 24h, and annealing the dried product at 500 ℃ to obtain hollow hexammine Co3O4A gas sensitive material.
6. The hollow hexammine Co-based material of claim 53O4The preparation method of the methanol sensor is characterized in that cobalt nitrate and ammonium fluoride are mixedStirring thoroughly at room temperature includes: the stirring time was 25min and the stirring speed was 500-.
7. The hollow hexammine Co-based material of claim 53O4The preparation method of the methanol sensor is characterized in that the hydrothermal reaction comprises the following steps: reacting for 6-25 h at 70-2000 ℃.
8. The hollow hexammine Co-based material of claim 53O4A method of making a methanol sensor of material, wherein the alternating centrifugation comprises: the time of each centrifugation is 8min, and the centrifugation speed is 400-1000 rpm.
9. The hollow hexammine Co-based material of claim 43O4The preparation method of the methanol sensor made of the material is characterized in that in the second step, the step of cleaning the alumina ceramic tube by using ethanol comprises the following steps: putting 3-5 ceramic tubes into a 100ml beaker simultaneously, and performing ultrasonic cleaning with ethanol and acetone alternately for six times, wherein the ultrasonic time is 10min each time;
the hollow hexagram-shaped Co to be prepared3O4The grinding and mixing of the gas sensitive material and the deionized water comprises the following steps:
0.02g of hollow hexagram-shaped Co3O4The gas sensitive material is put in a mortar, and then a dropper is used to gradually drop 2ml of deionized water, and the mixture is ground for 15s and mixed to form uniform slurry.
10. A gas sensor, characterized in that the gas sensor adopts the hollow hexammine Co-based sensor of any one of claims 1-23O4A methanol sensor of the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110585032.2A CN113447557B (en) | 2021-05-27 | 2021-05-27 | Based on hollow six mango star Co 3 O 4 Methanol sensor made of material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110585032.2A CN113447557B (en) | 2021-05-27 | 2021-05-27 | Based on hollow six mango star Co 3 O 4 Methanol sensor made of material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113447557A true CN113447557A (en) | 2021-09-28 |
| CN113447557B CN113447557B (en) | 2022-12-02 |
Family
ID=77810278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110585032.2A Active CN113447557B (en) | 2021-05-27 | 2021-05-27 | Based on hollow six mango star Co 3 O 4 Methanol sensor made of material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113447557B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249348A (en) * | 2011-05-26 | 2011-11-23 | 中国科学院青海盐湖研究所 | Method for preparing hexagonal plate cobaltosic oxide |
| CN104965008A (en) * | 2015-06-30 | 2015-10-07 | 江西师范大学 | Acetone gas sensor and preparation method thereof |
| CN105600838A (en) * | 2016-02-03 | 2016-05-25 | 天津大学 | Synthesis method for loading cobaltosic oxide on butterfly wings as biological template and application thereof |
| CN105699439A (en) * | 2016-02-25 | 2016-06-22 | 济南大学 | Preparation method and application of methanol gas sensor based on carbon nitride loaded metal and metal oxide composite |
| CN106770495A (en) * | 2016-12-08 | 2017-05-31 | 云南大学 | A kind of high selectivity methyl alcohol gas sensitive and preparation method and application |
| US20180224391A1 (en) * | 2015-07-31 | 2018-08-09 | Industry-University Cooperation Foundation Hanyang University Erica Campus | Multi-Layer Ceramic/Metal Type Gas Sensor And Manufacturing Method Of The Same |
| US20190224650A1 (en) * | 2017-12-29 | 2019-07-25 | Industry-Academic Cooperation Foundation, Yonsei University | Catalyst composite for conversion of methane gas and method for converting methane gas using the same |
| CN110068599A (en) * | 2019-05-31 | 2019-07-30 | 吉林大学 | One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials |
| CN110065972A (en) * | 2019-05-17 | 2019-07-30 | 河南师范大学 | One kind preparing hamburger shape Co by raw material of ZIF-673O4The method and its application of gas sensitive |
| CN111573744A (en) * | 2020-04-04 | 2020-08-25 | 西安电子科技大学 | Nickel cobaltate gas-sensitive material, nickel cobaltate gas-sensitive sensor and preparation method thereof |
| US20200270757A1 (en) * | 2019-02-26 | 2020-08-27 | King Fahd University Of Petroleum And Minerals | Cobalt oxide film upon electron sink |
| US20200338534A1 (en) * | 2019-04-28 | 2020-10-29 | Soochow University | Tricobalt tetraoxide dodecahedron / carbon nitride nanosheet composite and application thereof in exhaust gas treatment |
| CN112666230A (en) * | 2020-12-29 | 2021-04-16 | 西安电子科技大学 | Acetone sensor, preparation method and acetone detection method |
-
2021
- 2021-05-27 CN CN202110585032.2A patent/CN113447557B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249348A (en) * | 2011-05-26 | 2011-11-23 | 中国科学院青海盐湖研究所 | Method for preparing hexagonal plate cobaltosic oxide |
| CN104965008A (en) * | 2015-06-30 | 2015-10-07 | 江西师范大学 | Acetone gas sensor and preparation method thereof |
| US20180224391A1 (en) * | 2015-07-31 | 2018-08-09 | Industry-University Cooperation Foundation Hanyang University Erica Campus | Multi-Layer Ceramic/Metal Type Gas Sensor And Manufacturing Method Of The Same |
| CN105600838A (en) * | 2016-02-03 | 2016-05-25 | 天津大学 | Synthesis method for loading cobaltosic oxide on butterfly wings as biological template and application thereof |
| CN105699439A (en) * | 2016-02-25 | 2016-06-22 | 济南大学 | Preparation method and application of methanol gas sensor based on carbon nitride loaded metal and metal oxide composite |
| CN106770495A (en) * | 2016-12-08 | 2017-05-31 | 云南大学 | A kind of high selectivity methyl alcohol gas sensitive and preparation method and application |
| US20190224650A1 (en) * | 2017-12-29 | 2019-07-25 | Industry-Academic Cooperation Foundation, Yonsei University | Catalyst composite for conversion of methane gas and method for converting methane gas using the same |
| US20200270757A1 (en) * | 2019-02-26 | 2020-08-27 | King Fahd University Of Petroleum And Minerals | Cobalt oxide film upon electron sink |
| US20200338534A1 (en) * | 2019-04-28 | 2020-10-29 | Soochow University | Tricobalt tetraoxide dodecahedron / carbon nitride nanosheet composite and application thereof in exhaust gas treatment |
| CN110065972A (en) * | 2019-05-17 | 2019-07-30 | 河南师范大学 | One kind preparing hamburger shape Co by raw material of ZIF-673O4The method and its application of gas sensitive |
| CN110068599A (en) * | 2019-05-31 | 2019-07-30 | 吉林大学 | One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials |
| CN111573744A (en) * | 2020-04-04 | 2020-08-25 | 西安电子科技大学 | Nickel cobaltate gas-sensitive material, nickel cobaltate gas-sensitive sensor and preparation method thereof |
| CN112666230A (en) * | 2020-12-29 | 2021-04-16 | 西安电子科技大学 | Acetone sensor, preparation method and acetone detection method |
Non-Patent Citations (5)
| Title |
|---|
| BUSHRA SAFDAR 等: "Self-standing star-shaped tri-metallic oxides for pseudocapacitive energy storage electrode materials", 《APPLIED SURFACE SCIENCE》 * |
| JIAN-PING ZOU 等: "Electrochemical oxidation and advanced oxidation processes using a 3D hexagonal Co3O4 array anode for 4-nitrophenol decomposition coupled with simultaneous CO2 conversion to liquid fuels via a flower-like CuO cathode", 《WATER RESEARCH》 * |
| LI LI 等: "Self-assembly of hierarchical star-like Co3O4 micro/nanostructures and their application in lithium ion batteries", 《NANOSCALE》 * |
| 吉文哲等: "基于SmFeO_3纳米晶粒的甲醇传感器", 《仪表技术与传感器》 * |
| 汤春妮: "四氧化三钴的制备及应用研究进展", 《化学与生物工程》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113447557B (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | NH3 gas sensing performance enhanced by Pt-loaded on mesoporous WO3 | |
| David et al. | Room temperature operatable high sensitive toluene gas sensor using chemiresistive Ag/Bi2O3 nanocomposite | |
| Zhang et al. | Fabrication of Co3O4 nanowires assembled on the surface of hollow carbon spheres for acetone gas sensing | |
| CN108663417B (en) | One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive | |
| CN112666230A (en) | Acetone sensor, preparation method and acetone detection method | |
| Das et al. | A highly sensitive cobalt chromite thick film based trace acetone sensor with fast response and recovery times for the detection of diabetes from exhaled breath | |
| CN111848161A (en) | Preparation method of nano zirconia powder | |
| CN109437329A (en) | A kind of Co3O4/ graphene composite material and its preparation method and application | |
| CN110514700B (en) | Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method | |
| CN108956708A (en) | A kind of alcohol gas sensor and preparation method thereof based on zinc ferrite nano sensitive material | |
| CN113899790A (en) | Acetone sensor, preparation method and application | |
| CN110836913A (en) | Iron-doped porous indium oxide gas-sensitive material and preparation method and application thereof | |
| CN113447557B (en) | Based on hollow six mango star Co 3 O 4 Methanol sensor made of material, preparation method and application | |
| Ye et al. | Biotemplate-assisted synthesis of CuO hierarchical tubes for highly chemiresistive detection of dimethylamine at room temperature | |
| CN117069165A (en) | Preparation method of Pd modified two-dimensional porous NiO/ZnO gas-sensitive material and method for preparing CO gas sensor by using Pd modified two-dimensional porous NiO/ZnO gas-sensitive material | |
| Besprozvannykh et al. | Synthesis and Physicochemical Properties of Complex Oxides K 2 Me x Ti 8–x O 16 (Me= Mg, Ni, Al) of Hollandite Structure | |
| CN115676874A (en) | Metal-organic framework derived SnO 2 -ZnO compound gas-sensitive material and preparation method thereof | |
| Wang et al. | A MOF-derived porous In 2 O 3 flower-like hierarchical architecture sensor: near room-temperature preparation and fast trimethylamine sensing performance | |
| Hu et al. | Enhanced acetone sensing of MOFs derived Co3O4-ZIF hierarchical structure under the strategy of internal construction and external modification | |
| CN113433174A (en) | Ethanol sensor based on ZnO porous structure microsphere sensitive material, preparation method and application thereof | |
| CN110642288B (en) | Nitrogen-doped metal oxide gas-sensitive material, gas-sensitive element, and preparation method and application thereof | |
| CN107091863A (en) | A kind of three-layer laminated NiZnAl multichip semiconductors metal oxide composite and its preparation method and application | |
| CN113219010A (en) | Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation | |
| CN111721813A (en) | Based on tubulose SnO2Array acetone gas sensor and preparation method thereof | |
| CN113075266A (en) | NGQD/Fe2O3Graphene foam composite film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |