CN113433171A - Gas-sensitive material, gas-sensitive sensor, and preparation method and application thereof - Google Patents
Gas-sensitive material, gas-sensitive sensor, and preparation method and application thereof Download PDFInfo
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- CN113433171A CN113433171A CN202110707323.4A CN202110707323A CN113433171A CN 113433171 A CN113433171 A CN 113433171A CN 202110707323 A CN202110707323 A CN 202110707323A CN 113433171 A CN113433171 A CN 113433171A
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- 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
- G01N27/02—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
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- 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
- G01N27/02—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
- G01N27/041—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body
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- 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
- G01N27/02—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
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
Abstract
The invention provides a gas sensitive material, a gas sensitive sensor, a preparation method and an application thereof, and relates to the field of gas sensitive sensors. The preparation method of the gas-sensitive material comprises the following steps: oxidizing the foamed nickel to obtain a foamed nickel material with a nickel oxide layer on the surface; and (3) growing a zinc oxide nano array on the surface of the nickel oxide layer of the material obtained in the previous step to obtain the gas-sensitive material. Because the nickel resource reserves are abundant, the gas sensitive material and the gas sensitive sensor are prepared by taking the foam nickel as the raw material, and the preparation cost is low; the preparation method is simple, and the composition of the micron material and the nano material is realized; the gas-sensitive material and the sensor provided by the invention have excellent selectivity and higher sensitivity to the glycol gas, and can meet the requirement of glycol gas detection.
Description
Technical Field
The invention relates to the field of gas sensors, in particular to a gas sensitive material, a gas sensor, and a preparation method and application thereof.
Background
The development of the internet of things in China is in the early stage, and the development of the internet of things brings more and more convenience to our lives. The sensor plays a vital role in the development process of the Internet of things, and the sensor is similar to the Internet of things and is better than eyes, ears, nose, mouth, tongue and skin of a human body. Human beings rely on above bodily organs to go the perception environment, make appropriate reaction, and similarly, the thing networking is in order to go to perception object and environment around through the sensor to provide the basis for the data analysis of thing networking application layer.
As one of the sensors, a gas sensor is a transducer for converting a volume fraction of a certain gas into a corresponding electrical signal, and can be classified into: semiconductor gas sensors, electrochemical gas sensors, catalytic combustion gas sensors, thermal conductivity gas sensors, infrared gas sensors, solid electrolyte gas sensors, and the like. The semiconductor type gas sensor accounts for about 60% of the gas sensors, and is a hot spot of current research. Nickel oxide has been drawing attention as a typical p-type semiconductor material because it has advantages such as a low operating temperature and a high catalytic activity. The nickel reserves in China are rich, meanwhile, the foamed nickel has a three-dimensional net structure, the foamed nickel is used as a substrate, and a p-type nickel oxide layer is generated on the surface of the foamed nickel through oxidation, so that the detection of the ethylene glycol gas can be realized, but the sensitivity is low. At present, there are many methods for preparing semiconductor sensing materials, mainly including: electrostatic spinning, chemical vapor deposition, magnetron sputtering, and the like. However, the above synthetic methods all have the problems of high cost, complex preparation method, harsh experimental conditions and the requirement of experimental personnel to have certain experimental skills. Therefore, it is necessary to find a semiconductor sensing material for a gas sensor, which is low in cost, simple and effective, and has high sensitivity.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a gas-sensitive material, a gas-sensitive sensor, a preparation method and an application thereof, wherein the gas-sensitive material and the gas-sensitive sensor are convenient to prepare and low in cost and have higher sensitivity.
In a first aspect, the present invention provides a method for preparing a gas sensitive material, comprising:
(1) oxidizing the foamed nickel to obtain a foamed nickel material with a nickel oxide layer on the surface;
(2) and (2) growing a zinc oxide nano array on the surface of the nickel oxide layer of the material obtained in the step (1) to obtain the gas-sensitive material.
Further, in the step (1), the foamed nickel is cleaned and then put into a tube furnace for oxidation to obtain the foamed nickel material with the nickel oxide layer on the surface,
preferably, the oxidation conditions are: heating to 800-900 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-3 h, and cooling along with the furnace;
preferably, the method for cleaning the foamed nickel comprises: and (3) ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and drying.
Further, in the step (2), the method comprises the following steps: immersing the material obtained in the step (1) into a zinc oxide seed layer solution and a hydrothermal solution in sequence to obtain a nickel oxide-nickel foam material with a zinc oxide seed layer attached to the surface, carrying out heat treatment on the material to obtain the gas-sensitive material,
preferably, the material obtained in the step (1) is sequentially immersed in the zinc oxide seed layer solution and the hydrothermal solution for 30-60 seconds respectively, and dried, and the operations are repeated for 1-6 times to obtain the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface;
preferably, the heat treatment conditions are: putting the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 90-120 ℃ at the speed of 2-5 ℃/min, preserving the heat for 4-8 h, and naturally cooling to room temperature;
preferably, in the step (2), the method further comprises: washing the heat-treated material with absolute ethyl alcohol and deionized water successively, repeating the above operations for 1-3 times, and drying the washed material in a constant-temperature drying oven at 60-80 ℃.
Further, the preparation method of the zinc oxide seed layer solution comprises the following steps: respectively dissolving zinc acetate dihydrate and hexamethylenetetramine in deionized water to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, uniformly stirring to obtain the zinc oxide seed layer solution,
preferably, the mass-to-volume ratio of the zinc acetate dihydrate to the deionized water is 0.06-0.07 g/mL, preferably 0.06569 g/mL; the mass-volume ratio of the hexamethylenetetramine to the deionized water is 0.04-0.05 g/mL, preferably 0.04253 g/mL; the volume ratio of the zinc acetate dihydrate solution to the hexamethylenetetramine solution is 1: 1-1.5.
Further, the preparation method of the hydrothermal solution comprises the following steps: dissolving zinc nitrate in deionized water, and uniformly stirring; adding hexamethylene tetramine, and stirring uniformly; ammonia water is dripped, the solution turns turbid first and then becomes clear, the hydrothermal solution is obtained,
preferably, the mass volume ratio of the zinc nitrate to the deionized water is 0.02-0.025g/mL, and the mass volume ratio of the hexamethylenetetramine to the deionized water is 0.0028-0.003 g/mL.
In a second aspect, the invention provides a gas-sensitive material obtained by the above preparation method.
In a third aspect, the present invention provides a method for preparing a gas sensor, comprising:
(1) grinding the gas-sensitive material obtained by the preparation method and a binder to form slurry;
(2) coating the slurry prepared in the step (1) on the surface of a ceramic tube;
(3) and (3) drying and calcining the ceramic tube prepared in the step (2), and configuring a heating wire for the calcined ceramic tube, welding and packaging to obtain the gas sensor.
Further, in the step (1), the mass ratio of the gas-sensitive material to the binder is 0.5-1: 1; the binder comprises ethyl cellulose and terpineol in a mass ratio of 7-9: 1;
in the step (2), a stainless steel needle is used for coating;
in the step (3), the drying temperature is 60-80 ℃, and the calcining conditions are as follows: heating to 400-550 ℃ at the speed of 2-10 ℃/min, preserving heat for 2-5 h, and naturally cooling to room temperature.
In a fourth aspect, the invention provides a gas sensor obtained by the above preparation method.
In a fifth aspect, the invention provides an application of the gas sensitive material obtained by the preparation method or the gas sensor obtained by the preparation method in glycol gas detection.
The technical scheme of the invention has the following advantages:
1. the world nickel resource reserves are very rich, the nickel content in the earth core is highest, the gas sensitive material and the gas sensitive sensor are prepared by taking the foamed nickel as the raw material, and the preparation cost is low;
2. the preparation method is simple, and the composition of the micron material and the nano material is realized;
3. the gas-sensitive material and the sensor provided by the invention have excellent selectivity and higher sensitivity to the glycol gas, and can meet the requirement of glycol gas detection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron micrograph of a gas-sensitive material prepared in example 1;
FIG. 2 is a graph of baseline resistance versus temperature for gas sensors prepared in comparative examples, examples 1, 3, and 4;
FIG. 3 is a graph of the dynamic response of the gas sensors prepared in comparative example, examples 1, 3, 4 to 100ppm ethylene glycol at 175 ℃;
FIG. 4 shows the results of selectivity tests of the gas sensors prepared in comparative example, examples 1, 3 and 4 for ethanol, acetone, methanol, nitrogen dioxide, carbon monoxide, ammonia and ethylene glycol at 175 ℃;
FIG. 5 is a result of repeated tests of the gas sensor prepared in comparative example, examples 1 and 4 at 175 ℃ on 100ppm ethylene glycol for 5 times.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
Reagent and instrument sources
A ceramic tube: purchased from Zhengzhou Weisheng electronic technology Co.
Ethyl cellulose: purchased from Shanghai Aladdin Biotechnology Ltd.
Zinc acetate (molecular formula: C)4H6O4Zn·2H2O): purchased from metropolis chemicals, ltd.
Terpineol: purchased from Kaixin chemical industries, Inc., Tianjin.
Zinc nitrate (molecular formula: Zn (NO))3)2·6H2O): purchased from a chemical reagent factory of metropolis Kelong.
Hexamethylenetetramine: (formula: C)6H12N4) Purchased from Shuangshuang chemical Co., Ltd.
WS-30A gas sensor tester: purchased from Zhengzhou Weisheng electronic technology Co.
FGL-25/30/1 open tube furnace: purchased from fertilizer-and-fee Scholl thermal energy technology, Inc.
Electric heating constant temperature drying oven: purchased from health instruments, ltd.
Microsyringe: purchased from Shanghai Guangzhou medical instruments, Inc.
Nickel-chromium heating wire: purchased from Zhengzhou Weisheng electronic technology Co.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The raw materials or equipment used are all conventional products which can be obtained commercially, including but not limited to the raw materials or equipment used in the examples of the present application.
Example 1
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving the zinc oxide particles in 10mL of deionized water respectively, stirring for 15min by using a magnetic stirrer to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: 0.8008g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 40mL of deionized water and stirred with a magnetic stirrer for 20min, followed by addition of 0.1122g of hexamethylenetetramine (C)6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 3 times, so that a white substance is seen to be attached to the surface of the material, and the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface is obtained;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 6h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive material is shown in figure 1;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Example 2
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving the zinc oxide particles in 10mL of deionized water respectively, stirring for 15min by using a magnetic stirrer to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: 0.8008g of zinc nitrate (Zn (NO)3)2·6H2O) dissolved in 40mL to removeIn water and stirred with a magnetic stirrer for 20min, and 0.1122g of hexamethylenetetramine (C) was added to the solution6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 3 times, so that a white substance is seen to be attached to the surface of the material, and the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface is obtained;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 6h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Example 3
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving the zinc oxide particles in 10mL of deionized water respectively, stirring for 15min by using a magnetic stirrer to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: 0.8008g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 40mL of deionized water and stirred with a magnetic stirrer for 20min, followed by addition of 0.1122g of hexamethylenetetramine (C)6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 3 times, so that a white substance is seen to be attached to the surface of the material, and the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface is obtained;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 4h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive material is shown in figure 1;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Example 4
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving the zinc oxide particles in 10mL of deionized water respectively, stirring for 15min by using a magnetic stirrer to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: 0.8008g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 40mL of deionized water and stirred with a magnetic stirrer for 20min, followed by addition of 0.1122g of hexamethylenetetramine (C)6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 3 times, so that a white substance is seen to be attached to the surface of the material, and the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface is obtained;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 8h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive material is shown in figure 1;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Example 5
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving in 10mL deionized water respectively, stirring with magnetic stirrer for 15min to obtain zinc acetate dihydrate solution and hexamethylenetetramine solution, and mixingAdding the zinc acetate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: 0.8008g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 40mL of deionized water and stirred with a magnetic stirrer for 20min, followed by addition of 0.1122g of hexamethylenetetramine (C)6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 4 times, so that a white substance is seen to be attached to the surface of the material, and thus obtaining the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 6h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive material is shown in figure 1;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Example 6
A preparation method of a gas sensor comprises the following steps:
(1) oxidation of foamed nickel: and ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and then drying. Then, putting the cleaned foam nickel into a tubular furnace for oxidation, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then cooling along with the furnace to obtain a foam nickel material with a nickel oxide layer on the surface;
(2) preparing a zinc oxide seed layer solution: 0.6569g of zinc acetate dihydrate (C)4H6O4Zn·2H2O) and 0.4253g of hexamethylenetetramine (C)6H12N4) Dissolving the zinc oxide particles in 10mL of deionized water respectively, stirring for 15min by using a magnetic stirrer to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, and continuously stirring for 15min to obtain a zinc oxide seed layer solution;
(3) preparing a hydrothermal solution: o.8008g of zinc nitrate (Zn (NO)3)2·6H2O) was dissolved in 40mL of deionized water and stirred with a magnetic stirrer for 20min, followed by addition of 0.1122g of hexamethylenetetramine (C)6H12N4) Stirring uniformly, then slowly dripping ammonia water, and clarifying the solution after the solution becomes turbid to obtain a hydrothermal solution;
(4) preparing a zinc oxide seed layer: soaking the material obtained in the step (1) into the zinc oxide seed layer solution prepared in the step (2) for 30s, drying, soaking into the hydrothermal solution prepared in the step (3) for 30s, and drying, repeating the operation for 1 time, so that a white substance is seen to be attached to the surface of the material, and the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface is obtained;
(5) growing a zinc oxide nano-array: putting the nickel oxide-foamed nickel material with the zinc oxide seed layer attached to the surface, which is obtained in the step (4), into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 95 ℃ at the speed of 2 ℃/min, preserving the temperature for 6h, naturally cooling to room temperature to obtain a nickel oxide-foamed nickel material with a zinc oxide nano array growing on the surface, taking the nickel oxide-foamed nickel material out by using tweezers, washing the nickel oxide-foamed nickel material for 3 times by using absolute ethyl alcohol and deionized water, putting the nickel oxide-foamed nickel material into a constant-temperature drying oven at the temperature of 60 ℃ for drying to obtain a gas-sensitive material, wherein a scanning electron microscope image of the gas-sensitive material is shown in figure 1;
(6) preparing a gas sensor: and (3) placing the gas-sensitive material obtained in the step (5) in a mortar, adding a binder (the mass ratio of ethyl cellulose to terpineol is 9: 1), grinding to form uniform slurry, coating the slurry on the surface of a ceramic tube by using a stainless steel needle, placing the coated ceramic tube in a constant-temperature drying box at 60 ℃ for drying, then placing the coated ceramic tube in a tube furnace, calcining at high temperature to remove organic matters, heating to 450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, passing a nickel-cadmium heating wire through the ceramic tube, and welding and packaging according to a general indirectly-heated gas-sensitive element to obtain the gas-sensitive sensor.
Comparative example
This comparative example provides a gas sensor, which is different from example 1 only in that a gas sensor is produced by directly using the nickel foam material having a nickel oxide layer on the surface obtained in step (1) as a gas sensitive material, and the production method is referred to step (6) of example 1.
Test example 1
Baseline resistance of gas sensor at different temperatures:
all performance tests of the gas sensor are completed by a WS-30A gas sensor tester, the working temperature is changed by changing the voltage of the nickel-chromium heating wire, and the baseline resistance of the sensor is measured at different working temperatures. As shown in fig. 2, the baseline resistances of the gas sensors prepared in the comparative examples and examples 1, 3, and 4 at different temperatures were tested, and it was found that the baseline resistance gradually decreased with the increase in temperature, and the resistance change rule of the semiconductor metal oxide with the change in temperature was satisfied, confirming that the prepared gas sensors were of a semiconductor type.
Test example 2
Response of gas sensor to ethylene glycol gas:
a WS-30A gas-sensitive element tester is used for testing the gas-sensitive performance of the device at 175 ℃, the sensor is firstly exposed in the air atmosphere for 3-5 minutes, then a microsyringe is used for injecting gas to be tested with specific concentration into a cavity, and the device is exposed in the atmosphere after the gas reacts with the sensor sufficiently, so that a gas-sensitive response curve is obtained.
As shown in fig. 3, the gas sensors prepared in comparative examples 1, 3 and 4 were tested at 175 ℃ for 100ppm ethylene glycol, and the response of the gas sensors was found to be 59.98. The prepared gas sensor is proved to be capable of sensitively detecting glycol gas at a lower temperature and has excellent response characteristics.
Test example 3
Selectivity of the gas sensor to ethylene glycol gas:
in keeping with the conditions of test example 2, 7 interfering gases including ethylene glycol gas were tested at an optimum operating temperature of 175 ℃, and as shown in fig. 4, it was found that the gas sensors prepared in comparative example, examples 1, 3, and 4 responded to ethylene glycol gas significantly more than the other six interfering gases, and thus exhibited excellent selectivity to ethylene glycol gas.
Test example 4
Repeatability of gas sensor response to ethylene glycol gas:
consistent with the conditions of test example 2, five cycles of the gas sensors prepared in comparative examples 1 and 4 were tested at 175 ℃ in an atmosphere of 100ppm ethylene glycol, and the results are shown in fig. 5, which revealed that the sensors had good reproducibility and could be tested for multiple times in succession.
The combination of the above performance test results shows that the optimal working temperature of the gas sensor prepared by the embodiment of the invention is 175 ℃, the response to 100ppm of ethylene glycol gas at the optimal working temperature is 59.98, and the gas sensor has excellent selectivity and good repeatability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method of preparing a gas sensitive material, comprising:
(1) oxidizing the foamed nickel to obtain a foamed nickel material with a nickel oxide layer on the surface;
(2) and (2) growing a zinc oxide nano array on the surface of the nickel oxide layer of the material obtained in the step (1) to obtain the gas-sensitive material.
2. The method for preparing the gas-sensitive material according to claim 1, wherein in the step (1), the foamed nickel is cleaned and then put into a tube furnace for oxidation to obtain the foamed nickel material with the nickel oxide layer on the surface,
preferably, the oxidation conditions are: heating to 800-900 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-3 h, and cooling along with the furnace;
preferably, the method for cleaning the foamed nickel comprises: and (3) ultrasonically cleaning the foamed nickel by using acetone, alcohol and deionized water in sequence, and drying.
3. The method for producing a gas-sensitive material according to claim 1 or 2, wherein in the step (2), the method comprises: immersing the material obtained in the step (1) into a zinc oxide seed layer solution and a hydrothermal solution in sequence to obtain a nickel oxide-nickel foam material with a zinc oxide seed layer attached to the surface, carrying out heat treatment on the material to obtain the gas-sensitive material,
preferably, the material obtained in the step (1) is sequentially immersed into the zinc oxide seed layer solution and the hydrothermal solution for 30-60 seconds respectively, and dried, and the operations are repeated for 1-6 times to obtain the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface;
preferably, the heat treatment conditions are: putting the nickel oxide-nickel foam material with the zinc oxide seed layer attached to the surface into a hydrothermal kettle, then putting the hydrothermal kettle into an oven, heating to 90-120 ℃ at the speed of 2-5 ℃/min, preserving the heat for 4-8 h, and naturally cooling to room temperature;
preferably, in the step (2), the method further comprises: and washing the heat-treated material with absolute ethyl alcohol and deionized water successively, repeating the operation for 1-3 times, and drying the washed material in a constant-temperature drying box at 60-80 ℃.
4. The method for producing a gas-sensitive material according to claim 3,
the preparation method of the zinc oxide seed layer solution comprises the following steps: respectively dissolving zinc acetate dihydrate and hexamethylenetetramine in deionized water to obtain a zinc acetate dihydrate solution and a hexamethylenetetramine solution, adding the zinc acetate dihydrate solution into the hexamethylenetetramine solution, uniformly stirring to obtain the zinc oxide seed layer solution,
preferably, the mass-to-volume ratio of the zinc acetate dihydrate to the deionized water is 0.06-0.07 g/mL, preferably 0.06569 g/mL; the mass-volume ratio of the hexamethylenetetramine to the deionized water is 0.04-0.05 g/mL, preferably 0.04253 g/mL; the volume ratio of the zinc acetate dihydrate solution to the hexamethylenetetramine solution is 1: 1-1.5.
5. The method for producing a gas-sensitive material according to claim 3,
the preparation method of the hydrothermal solution comprises the following steps: dissolving zinc nitrate in deionized water, and uniformly stirring; adding hexamethylene tetramine, and stirring uniformly; ammonia water is dripped, the solution turns turbid first and then becomes clear, the hydrothermal solution is obtained,
preferably, the mass volume ratio of the zinc nitrate to the deionized water is 0.02-0.025g/mL, and the mass volume ratio of the hexamethylenetetramine to the deionized water is 0.0028-0.003 g/mL.
6. A gas-sensitive material obtained by the production method according to any one of claims 1 to 5.
7. A method of making a gas sensor, comprising:
(1) grinding the gas-sensitive material obtained by the preparation method of any one of claims 1 to 5 and a binder to form slurry;
(2) coating the slurry prepared in the step (1) on the surface of a ceramic tube;
(3) and (3) drying and calcining the ceramic tube prepared in the step (2), and configuring a heating wire for the calcined ceramic tube, welding and packaging to obtain the gas sensor.
8. The method of manufacturing a gas sensor according to claim 7,
in the step (1), the mass ratio of the gas-sensitive material to the binder is 0.5-1: 1; the binder comprises ethyl cellulose and terpineol in a mass ratio of 7-9: 1;
in the step (2), a stainless steel needle is used for coating;
in the step (3), the drying temperature is 60-80 ℃, and the calcining conditions are as follows: heating to 400-550 ℃ at the speed of 2-10 ℃/min, preserving heat for 2-5 h, and naturally cooling to room temperature.
9. A gas sensor obtained by the production method according to claim 7 or 8.
10. The gas-sensitive material obtained by the preparation method of any one of claims 1 to 5 or the gas-sensitive sensor obtained by the preparation method of claim 7 or 8 is applied to detection of ethylene glycol gas.
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