CN109342523B - Resistance type NO2Sensor, preparation method and application thereof - Google Patents
Resistance type NO2Sensor, preparation method and application thereof Download PDFInfo
- Publication number
- CN109342523B CN109342523B CN201811200151.6A CN201811200151A CN109342523B CN 109342523 B CN109342523 B CN 109342523B CN 201811200151 A CN201811200151 A CN 201811200151A CN 109342523 B CN109342523 B CN 109342523B
- Authority
- CN
- China
- Prior art keywords
- composite material
- tin dioxide
- graphene oxide
- solution
- oxygen vacancy
- 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.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002131 composite material Substances 0.000 claims abstract description 98
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000001301 oxygen Substances 0.000 claims abstract description 87
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 76
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007650 screen-printing Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- -1 tin dioxide modified graphene Chemical class 0.000 abstract description 54
- 239000007789 gas Substances 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000004528 spin coating Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 description 14
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 11
- 238000011084 recovery Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/304—Gas permeable electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Resistance type NO based on oxygen vacancy-rich tin dioxide modified graphene composite material2A sensor, a preparation method and an application thereof belong to the technical field of gas sensors. Ceramic wafer is used as a substrate, a carbon interdigital electrode is deposited on the surface of the ceramic wafer substrate by adopting a screen printing technology, and the carbon interdigital electrode isThe electrode is connected with a lead, and the surfaces of the ceramic chip substrate and the carbon interdigital electrode are coated with gas sensitive films which are made of oxygen vacancy-rich stannic oxide modified graphene composite materials. According to the invention, the tin dioxide nano particles are generated on the surface of the graphene by a wet chemical method, so that the combination of the tin dioxide and the carbon-based material can be obviously improved, the room-temperature conductivity of the material is improved, and the room-temperature detection is favorably realized. The prepared composite material solution can be formed into a film on the interdigital electrode by methods such as spin coating and the like, is easy to process, can be used for conveniently preparing the gas sensor, and solves the problems that the traditional metal oxide gas sensor needs high-temperature sintering and is complex to process.
Description
Technical Field
The invention belongs to the technical field of gas sensors, particularly relates to a graphene-based resistance type gas sensor with room-temperature gas-sensitive response characteristic and a manufacturing method thereof, and particularly relates to resistance type NO based on oxygen vacancy-rich tin dioxide modified graphene composite material2Sensor, preparation method and application thereof in detecting NO2The use of (1).
Background
With the rapid development of industry and agriculture and the continuous increase of the keeping quantity of motor vehicles, the discharge amount of nitrogen oxides is increased day by day, the natural environment and the human health are seriously damaged, and the problem of environmental pollution is more and more prominent. Accurate and continuous detection of nitrogen oxides in the environment becomes an urgent problem to be solved, and a wide space is provided for application of the gas sensor. The gas sensor is an important chemical sensor and has wide application in the fields of industrial and agricultural production, process control, environmental monitoring and protection, anti-terrorism and the like. Development of high-performance NO with the advantages of high sensitivity, low cost, low power consumption, miniaturization and the like2Gas sensors have become a research hotspot in the scientific research field and the industrial field.
At present, semiconductor oxides typified by tungsten trioxide and indium trioxide are most usedIs a wide class of sensitive materials, and has the advantages of convenient preparation, low cost, wide source and the like. Due to the pair of NO2Exhibits excellent sensitivity, and tungsten trioxide and indium trioxide are widely used for constructing resistive NO2A sensor. However, these devices also have some disadvantages, such as poor stability, high influence by humidity, and less than ideal selectivity. Especially, the metal oxide based gas sensor needs to operate at a higher temperature, which causes the power consumption of the element to be large, and makes it difficult to prepare a portable instrument, so that the application thereof is limited.
In order to solve this problem, researchers have paid extensive attention to the development of gas sensitive materials that operate at room temperature by lowering the operating temperature of the sensor. In recent years, two-dimensional carbon-based nanomaterials represented by graphene have been developed rapidly, and become a hot spot of research in the material field. The room-temperature conductivity and the fast carrier mobility of the graphene provide a new idea for developing gas sensitive materials working at room temperature. Researches find that the graphene material can really detect gas at room temperature, but the manufactured sensor has low sensitivity and slow response recovery rate. Recently, the graphene is modified by metal oxide nanoparticles with excellent sensitivity, and the sensitivity and the response recovery rate of the graphene-based gas sensor can be further improved by utilizing the oxygen-containing functional groups on the rich surface of the metal oxide. By regulating the structure of the metal oxide nanoparticles, the synergistic effect of the metal oxide and the graphene is fully exerted, and high-sensitivity gas detection at room temperature is expected to be realized. The development of graphene-based room temperature gas sensors is one of the important directions for the research of the sensor field, and the development is very rapid.
Disclosure of Invention
It is an object of the present invention to provide an NO having a high sensitivity at room temperature2Resistance type NO based on oxygen vacancy-rich tin dioxide modified graphene composite material with response characteristic2Sensor, preparation method and application thereof in detecting NO2The use of (1).
The invention relates to resistance type NO based on oxygen vacancy-rich tin dioxide modified graphene composite material2Sensor, in the form of ceramicThe ceramic chip is taken as a substrate, carbon interdigital electrodes are deposited on the surface of the ceramic chip substrate by adopting a screen printing technology, the thickness of the electrodes is 1-2 mu m, the number of pairs of the electrodes is 4-6, and the width of each electrode is 50-100 mu m; a lead is connected to the carbon interdigital electrode, a gas sensitive film is coated on the surface of the ceramic chip substrate and the surface of the carbon interdigital electrode, the gas sensitive film is a tin dioxide modified graphene composite material rich in oxygen vacancies, and the thickness of the film is 10-50 mu m; before and after the gas sensitive film contacts the gas to be measured, the resistance of the gas sensitive film changes, a 1V voltage is applied to two ends of the carbon electrode by using an electrochemical analyzer (CHI, 660D, Shanghai Chenghua apparatus Co., Ltd.), the sensitivity of the sensor can be obtained by measuring the change of the current between the carbon interdigital electrodes, and the calculation method of the sensitivity is that the change value of the current of the carbon electrode in the air and the target gas is divided by the current value of the carbon electrode in the air. The oxygen vacancy-enriched tin dioxide modified graphene composite material is prepared by mixing (surface loading) graphene and tin dioxide, and the mass ratio of the graphene to the tin dioxide is 1: 3.6 to 12; the distribution of oxygen elements in the composite material is analyzed by adopting X-ray photoelectron spectroscopy, and the composite material is found to contain rich oxygen vacancies, wherein the content of the oxygen vacancies accounts for 30-50% of the total oxygen elements.
The invention relates to resistance type NO based on oxygen vacancy-rich tin dioxide modified graphene composite material2The preparation method of the sensor comprises the following steps:
(1) taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 1-2 mu m, the number of pairs of the electrodes is 4-6, and the width of each electrode is 50-100 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.1-5 mg/mL, and carrying out hydrothermal reaction on 30-40 mL of the solution at 160-180 ℃ for 12-24 hours to obtain a reduced graphene oxide solution;
(4) and (3) adding 0.012 g-0.24 g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 1.5-5: 250 to 12500; carrying out hydrothermal reaction on the solution at 160-180 ℃ for 12-24 hours to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 3.6 to 12; the composite material contains abundant oxygen vacancies, and the content of the oxygen vacancies is 30 to 50 percent;
(5) dispersing the oxygen vacancy-enriched tin dioxide modified graphene composite material prepared in the step (4) into water, wherein the concentration of the composite material is 1-10 mg/mL; the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode obtained in the step (2) in a suspension manner, then heat treatment is carried out for 1-4 hours at the temperature of 80-130 ℃, the thickness of the obtained sensitive film is 10-50 mu m, and therefore the resistance type NO based on the oxygen vacancy-rich stannic oxide modified graphene composite material is prepared2A sensor.
The gas sensor prepared by the invention is used for NO2Room temperature response of (1), NO2Is not more than 20ppm, preferably not less than 1ppm, and has a sensitivity of 16.94%. The lowest detectable concentration is 1 ppm. (NO in the patent)2The detection concentration of (1) to (20 ppm).
The invention has the advantages that:
1) the interdigital electrode is prepared by adopting a screen printing technology, so that the cost is low, the structure is easy to regulate and control, and the product consistency is high; the strong pi-pi action between the carbon electrode and the graphene material can improve the adhesion between the sensitive film and the electrode and improve the stability of the device.
2) The oxygen vacancy-enriched tin dioxide modified graphene composite material is prepared by a wet chemical method, and the method is simple, easy to operate and low in cost. And the regulation and control of the properties of the graphene-based composite material such as the composition, the structure and the like can be realized by controlling experimental parameters such as the reaction temperature, the reaction time, the proportion of the reaction precursor and the like.
3) The introduction of tin dioxide in the composite material can further prevent the agglomeration of graphene sheet layers, and effectively improve the specific surface area of the composite material.
4) The introduction of the graphene in the composite material can remarkably improve the conductivity of the sensitive material, and avoid the problem that the gas detection at room temperature cannot be realized due to overhigh room-temperature resistance and extremely low response sensitivity of the common tin dioxide.
5) The tin dioxide nano particles in the composite material are modified on the surface of graphene, and the surface active site is regulated and controlled by virtue of tin dioxide surface active sites and abundant oxygen vacancies, so that the sensitivity of the sensor is improved.
6) The tin dioxide nano particles are generated on the surface of the graphene by adopting a wet chemical method, so that the combination of the tin dioxide and the carbon-based material can be obviously improved, the room-temperature conductivity of the material is improved, and the room-temperature detection is facilitated. The prepared composite material solution can be formed into a film on the interdigital electrode by methods such as spin coating and the like, is easy to process, can be used for conveniently preparing the gas sensor, and solves the problems that the traditional metal oxide gas sensor needs high-temperature sintering and is complex to process.
Drawings
Fig. 1 is a schematic view of the structure of the gas sensor of the present invention. Wherein: ceramic wafer substrate 1, carbon interdigital electrodes 2 and 3, gas sensitive film 4, and leads 5 and 6.
FIG. 2 is an X-ray diffraction spectrum of the oxygen vacancy-rich tin dioxide modified graphene composite material.
FIG. 3 is a transmission electron microscope photograph of the oxygen vacancy-rich tin dioxide modified graphene composite material.
FIG. 4 is an X-ray photoelectron spectrum of the oxygen vacancy-rich tin dioxide modified graphene composite material.
FIG. 5 shows that the oxygen vacancy-rich stannic oxide modified graphene composite material gas sensor is used for measuring 1 ppm-20 ppm NO2Room temperature dynamic response recovery curve.
FIG. 6 is a bar graph of selectivity of a tin dioxide modified graphene composite material gas sensor rich in oxygen vacancies to different gases.
FIG. 7 is a response recovery curve of an oxygen vacancy-rich tin dioxide modified graphene composite gas sensor to 5ppm nitrogen dioxide at room temperature.
Detailed Description
The invention is further illustrated below with reference to the figures and examples.
Example 1
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 1 mu m, the number of pairs of the electrodes is 4, and the width of each electrode is 50 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.1mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 30mL at 160 ℃ for 12 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.012g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 5: 12500; carrying out hydrothermal reaction on the solution at 180 ℃ for 24 hours to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 12; the composite material contains abundant oxygen vacancies, and the content of the oxygen vacancies is 30 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 1 mg/mL; and (3) the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode in a suspension manner in the step (2), and a sensitive material film is obtained after heat treatment for 4 hours at the temperature of 80 ℃, wherein the thickness of the film is 10 mu m, so that the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material is prepared.
Example 2
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 1 mu m, the number of pairs of the electrodes is 4, and the width of each electrode is 50 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.5mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 30mL at 160 ℃ for 12 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.024g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution and the stannic chloride with water in a mass ratio of 1: 2: 150 to 2500; carrying out hydrothermal reaction on the solution at 180 ℃ for 24 hours to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 4.8; the composite material contains rich oxygen vacancies, and the content of the oxygen vacancies is 32 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 2.5 mg/mL; and (3) the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode in a suspension manner in the step (2), and a sensitive material film is obtained after heat treatment for 1 hour at the temperature of 90 ℃, wherein the thickness of the film is 20 mu m, so that the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material is prepared.
Example 3
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 1 mu m, the number of pairs of the electrodes is 5, and the width of each electrode is 70 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 1mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 30mL at 170 ℃ for 18 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.048g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 2: 470, respectively; carrying out hydrothermal reaction on the solution at 170 ℃ for 18 hours to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-containing tin dioxide modified graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 4.8; the composite material contains rich oxygen vacancies, and the content of the oxygen vacancies is 35 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 5 mg/mL; and (3) the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode in a suspension manner in the step (2), and a sensitive material film is obtained after heat treatment for 2 hours at the temperature of 100 ℃, wherein the thickness of the film is 30 mu m, so that the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material is prepared.
Example 4
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 2 mu m, the number of pairs of the electrodes is 5, and the width of each electrode is 70 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 40mL at 170 ℃ for 18 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.096g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 1.5: 625, carrying out hydrothermal reaction on the solution at 170 ℃ for 18 hours to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-rich tin dioxide modified graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 3.6; the composite material contains rich oxygen vacancies, and the content of the oxygen vacancies is 40 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 5 mg/mL; and (3) the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode in a suspension manner in the step (2), and a sensitive material film is obtained after heat treatment for 2 hours at the temperature of 110 ℃, wherein the thickness of the film is 40 mu m, so that the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material is prepared.
Example 5
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 2 mu m, the number of pairs of the electrodes is 6, and the width of each electrode is 100 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 2.5mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 40mL at 180 ℃ for 24 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.12g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 1.5: 500, a step of; carrying out hydrothermal reaction on the solution at 160 ℃ for 12 hours to prepare a stannic oxide modified graphene composite material solution rich in oxygen vacancies, carrying out centrifugal separation, washing and drying on the composite material solution to obtain the stannic oxide modified graphene composite material rich in oxygen vacancies, wherein the mass ratio of graphene to stannic oxide is 1: 3.6; the composite material contains rich oxygen vacancies, and the content of the oxygen vacancies is 45 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 7.5 mg/mL; and (3) carrying out heat treatment at 120 ℃ for 4 hours to obtain a sensitive material film, wherein the thickness of the film is 45 micrometers, and thus obtaining the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material.
Example 6
(1) Taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 2 mu m, the number of pairs of the electrodes is 6, and the width of each electrode is 100 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 5mg/mL, and carrying out hydrothermal reaction on the solution with the volume of 40mL at 180 ℃ for 24 hours to prepare a reduced graphene oxide solution;
(4) and (3) adding 0.24g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 1.5: 250 of (a); carrying out hydrothermal reaction on the solution at 160 ℃ for 12 hours to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-containing tin dioxide/graphene composite material, wherein the mass ratio of graphene to tin dioxide is 1: 3.6; the composite material contains abundant oxygen vacancies, and the content of the oxygen vacancies is 50 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified graphene composite material prepared in the step (4) into water to prepare an oxygen vacancy-rich tin dioxide modified graphene composite material aqueous solution, wherein the concentration of the composite material is 10 mg/mL; and (3) the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode in a suspension manner in the step (2), and a sensitive material film is obtained after heat treatment for 4 hours at the temperature of 130 ℃, wherein the thickness of the film is 50 mu m, so that the resistance type gas sensor based on the oxygen vacancy-rich tin dioxide modified graphene composite material is prepared.
The X-ray diffraction spectrum of the oxygen vacancy enriched tin dioxide modified graphene composite material prepared in the example 1 is shown in FIG. 2, and as can be seen from FIG. 2, the composite material has typical diffraction peaks attributed to tin dioxide, which indicates that the composite material contains tin dioxide.
A transmission electron micrograph of the oxygen vacancy enriched tin dioxide modified graphene composite material prepared in example 1 is shown in fig. 3. As can be seen from fig. 3, the tin dioxide nanoparticles are uniformly dispersed on the surface of the graphene sheet.
The X-ray photoelectron spectrum of the oxygen vacancy enriched tin dioxide modified graphene composite material prepared in example 1 is shown in fig. 4, and as can be seen from fig. 4, the composite material contains a large amount of vacancy oxygen, and the content of the vacancy oxygen is 30% of the total oxygen element content.
The response recovery curves of the oxygen vacancy enriched tin dioxide modified graphene-based composite material gas sensor prepared in example 1 at room temperature for different concentrations of nitrogen dioxide are shown in fig. 5. It can be seen that the prepared graphene-based gas sensor has high and quick response to nitrogen dioxide with different concentrations, the response time is less than 1 minute, and the sensor has good reversibility.
The selectivity of the response of the gas sensor based on the oxygen vacancy enriched tin dioxide modified graphene composite prepared in example 1 to 5ppm of different gases at room temperature is shown in fig. 6. It can be seen that the sensor pair NO2Exhibit excellent selectivity.
The response recovery curve of the oxygen vacancy enriched tin dioxide modified graphene-based composite material gas sensor prepared in example 2 at room temperature to 5ppm nitrogen dioxide is shown in fig. 7. It can be seen that the prepared graphene-based gas sensor has good response recovery characteristics to 5ppm nitrogen dioxide.
Claims (3)
1. Resistance type NO based on oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material2The preparation method of the sensor comprises the following steps:
(1) taking a ceramic wafer as a substrate, depositing carbon interdigital electrodes on the surface of the ceramic wafer by adopting a screen printing technology, wherein the thickness of the electrodes is 1-2 mu m, the number of pairs of the electrodes is 4-6, and the width of each electrode is 50-100 mu m;
(2) ultrasonically cleaning a ceramic wafer substrate with carbon interdigital electrodes on the surface by using ethanol and water in sequence, and drying;
(3) preparing a graphene oxide aqueous solution, wherein the concentration of the graphene oxide aqueous solution is 0.1-5 mg/mL, and carrying out hydrothermal reaction on 30-40 mL of the solution at 160-180 ℃ for 12-24 hours to obtain a reduced graphene oxide solution;
(4) and (3) adding 0.012 g-0.24 g of stannic chloride into the reduced graphene oxide solution prepared in the step (3), and performing ultrasonic dispersion to fully mix the reduced graphene oxide solution, the stannic chloride and water in a mass ratio of 1: 1.5-5: 250 to 12500; carrying out hydrothermal reaction on the solution at 160-180 ℃ for 12-24 hours to obtain an oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material solution, carrying out centrifugal separation, washing and drying on the composite material solution to obtain an oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material, wherein the mass ratio of the reduced graphene oxide to the tin dioxide is 1: 3.6 to 12; the composite material contains abundant oxygen vacancies, and the content of the oxygen vacancies is 30 to 50 percent;
(5) dispersing the oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material prepared in the step (4) into water, wherein the concentration of the composite material is 1-10 mg/mL; the solution is coated on the surface of the ceramic wafer substrate with the carbon interdigital electrode obtained in the step (2) in a suspension manner, then heat treatment is carried out for 1-4 hours at the temperature of 80-130 ℃, the thickness of the obtained sensitive film is 10-50 mu m, and therefore the resistance type NO based on the oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material is prepared2A sensor.
2. Resistance type NO based on oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material2A sensor, characterized by: is prepared by the method of claim 1.
3. The oxygen vacancy-rich tin dioxide modified reduced graphene oxide composite material-based resistive NO of claim 22Sensor detecting NO2The use of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811200151.6A CN109342523B (en) | 2018-10-16 | 2018-10-16 | Resistance type NO2Sensor, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811200151.6A CN109342523B (en) | 2018-10-16 | 2018-10-16 | Resistance type NO2Sensor, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109342523A CN109342523A (en) | 2019-02-15 |
| CN109342523B true CN109342523B (en) | 2020-02-14 |
Family
ID=65310423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811200151.6A Expired - Fee Related CN109342523B (en) | 2018-10-16 | 2018-10-16 | Resistance type NO2Sensor, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109342523B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110174448A (en) * | 2019-07-01 | 2019-08-27 | 哈尔滨理工大学 | A kind of electromagnetism interference type thermal conductivity gas sensor chip and preparation method thereof |
| CN110243881B (en) * | 2019-07-16 | 2020-07-31 | 东北大学 | Based on rGO-SnO2NO of nanocomposite2Gas sensor and preparation method thereof |
| CN111024777B (en) * | 2019-12-25 | 2022-07-12 | 广州钰芯传感科技有限公司 | Tin oxide modified sensor, preparation method thereof and application thereof in gas-sensitive detection of nitric oxide |
| CN111948261A (en) * | 2020-07-27 | 2020-11-17 | 浙江泰仑电力集团有限责任公司 | Gas sensitive element for on-line monitoring of power equipment fault characteristic gas and preparation method thereof |
| CN113325041B (en) * | 2021-05-31 | 2022-10-04 | 吉林大学 | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof |
| CN114014313B (en) * | 2022-01-06 | 2022-03-22 | 河北化工医药职业技术学院 | Graphene-based gas-sensitive material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102636522A (en) * | 2012-03-29 | 2012-08-15 | 浙江大学 | Graphene/ stannic oxide nanometer compounding resistance type film gas sensor and manufacturing method thereof |
| CN105891271B (en) * | 2016-03-31 | 2018-08-07 | 吉林大学 | It is a kind of based on graphene/resistor-type gas sensor of stannic oxide/zinc oxide composite, preparation method and applications |
| CN105883906B (en) * | 2016-04-11 | 2017-12-05 | 同济大学 | A kind of nano-stannic oxide and graphene composite material and preparation method and application |
| CN106219537B (en) * | 2016-08-30 | 2018-04-13 | 安徽师范大学 | A kind of preparation method of stannic oxide/graphene composite material, resistor-type gas sensor |
| CN106872533B (en) * | 2017-04-17 | 2020-02-04 | 吉林大学 | Resistance type acetone sensor based on graphitized nitrogen carbide/tin dioxide composite material, preparation method and application thereof |
| CN106990142A (en) * | 2017-05-09 | 2017-07-28 | 大连理工大学 | A kind of NO based on graphene/tin dioxide quantal-point composite2Sensor and preparation method thereof |
-
2018
- 2018-10-16 CN CN201811200151.6A patent/CN109342523B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109342523A (en) | 2019-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109342523B (en) | Resistance type NO2Sensor, preparation method and application thereof | |
| Song et al. | Fabrication of highly sensitive and selective room-temperature nitrogen dioxide sensors based on the ZnO nanoflowers | |
| Bo et al. | Decoration of vertical graphene with tin dioxide nanoparticles for highly sensitive room temperature formaldehyde sensing | |
| Li et al. | Coaxial electrospinning heterojunction SnO2/Au-doped In2O3 core-shell nanofibers for acetone gas sensor | |
| Li et al. | Ethanol sensing properties and reduced sensor resistance using porous Nb2O5-TiO2 nn junction nanofibers | |
| Liu et al. | Improved selective acetone sensing properties of Co-doped ZnO nanofibers by electrospinning | |
| CN109342522B (en) | Polypyrrole/graphene composite material-based resistance type NH3Sensor, preparation method and application thereof | |
| Dong et al. | A novel coral-shaped Dy2O3 gas sensor for high sensitivity NH3 detection at room temperature | |
| Guo et al. | Sensing platform of PdO-ZnO-In2O3 nanofibers using MOF templated catalysts for triethylamine detection | |
| Yin et al. | Synthesis of thickness-controlled cuboid WO3 nanosheets and their exposed facets-dependent acetone sensing properties | |
| Ge et al. | Ag/SnO2/graphene ternary nanocomposites and their sensing properties to volatile organic compounds | |
| Li et al. | Metal-organic framework-derived ZnO decorated with CuO for ultra-high response and selectivity H2S gas sensor | |
| Park et al. | Synthesis of self-bridged ZnO nanowires and their humidity sensing properties | |
| Qi et al. | Influence of crystallographic structure on the humidity sensing properties of KCl-doped TiO2 nanofibers | |
| Yi et al. | A novel approach to fabricate metal oxide nanowire-like networks based coplanar gas sensors array for enhanced selectivity | |
| Li et al. | High-response and low-temperature nitrogen dioxide gas sensor based on gold-loaded mesoporous indium trioxide | |
| Wang et al. | Fabrication and properties of room temperature ammonia gas sensor based on SnO2 modified WSe2 nanosheets heterojunctions | |
| Liu et al. | Construction of hollow NiO/ZnO pn heterostructure for ultrahigh performance toluene gas sensor | |
| Liu et al. | Synthesis, Characterization, and m‐Xylene Sensing Properties of Co–ZnO Composite Nanofibers | |
| Wang et al. | Methanol sensing properties of honeycomb-like SnO2 grown on silicon nanoporous pillar array | |
| Zhao et al. | Synthesis and gas sensing properties of NiO/ZnO heterostructured nanowires | |
| US20230124633A1 (en) | Self-heating gas sensor, gas-sensitive material, preparation method for same, and applications thereof | |
| Shen et al. | Highly sensitive ethanol gas sensor based on In 2 O 3 spheres | |
| Zhang et al. | A novel humidity sensor based on Na2Ti3O7 nanowires with rapid response-recovery | |
| He et al. | Synthesis of porous ZnFe2O4/SnO2 core-shell spheres for high-performance acetone gas sensing |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200214 |