CN109342523A - Based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor, preparation method and applications - Google Patents
Based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor, preparation method and applications Download PDFInfo
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- CN109342523A CN109342523A CN201811200151.6A CN201811200151A CN109342523A CN 109342523 A CN109342523 A CN 109342523A CN 201811200151 A CN201811200151 A CN 201811200151A CN 109342523 A CN109342523 A CN 109342523A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
It is a kind of based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistor-type NO2Sensor, preparation method and applications, belong to gas sensor technical field.It is using potsherd as substrate, carbon interdigital electrode is deposited in potsherd substrate surface using screen printing technique, lead is connected in carbon interdigital electrode, it is coated with gas-sensitive film in potsherd substrate and carbon interdigital electrode surface, which is rich in the grapheme modified composite material of Lacking oxygen stannic oxide.The present invention generates tin dioxide nano-particle using wet chemistry method on the surface of graphene, can significantly improve the combination of stannic oxide and carbon-based material, improve the conductivity at room temperature of material, is advantageously implemented room temperature detection.The composite material solution of preparation can be formed a film in interdigital electrode using the methods of spin coating, easy to process, prepare gas sensor with can be convenient, solve traditional metal-oxide gas transducer and need high temperature sintering, process complicated problem.
Description
Technical field
The invention belongs to gas sensor technical fields, and in particular to a kind of graphene with room temperature air-sensitive response characteristic
Based resistance type gas sensor and preparation method thereof, more particularly to one kind based on grapheme modified rich in Lacking oxygen stannic oxide
The resistor-type NO of composite material2Sensor, preparation method and its detection NO2In application.
Background technique
With the fast development of industrial or agricultural and the sustainable growth of vehicle guaranteeding organic quantity, the discharge amount of nitrogen oxides increasingly increases
Add, seriously destroy natural environment and human health, the problem of environmental pollution of generation is more and more prominent.To the nitrogen oxidation in environment
Object carries out, and accurate, continuous detection becomes urgent problem to be solved, this just provides wide sky for the application of gas sensor
Between.Gas sensor is a kind of important chemical sensor, in industrial and agricultural production, process control, environmental monitoring and protection and instead
Probably equal fields have a wide range of applications.Developing has many advantages, such as high sensitivity, low cost, low-power consumption, the high-performance NO minimized2
Gas sensor becomes the research hotspot of scientific research field and industrial circle.
Currently, becoming the most widely used one kind using tungstic acid, indium sesquioxide as the conductor oxidate of representative
Sensitive material has many advantages, such as that preparation is convenient, low in cost, from a wealth of sources.Due to NO2Show excellent sensibility
Can, tungstic acid and indium sesquioxide are widely used in constructing resistor-type NO2Sensor.But these devices there is also it is some not
Foot, for example, stability is poor, is affected by humidity, and selectivity is not ideal enough etc..It is based particularly on the gas of metal oxide
Sensor requires to work at a higher temperature, this makes the power consumption of element larger, it is difficult to prepare portable instrument, answer it
With being subject to certain restrictions.
In order to solve this problem, the operating temperature for reducing sensor, the gas sensitive for developing working and room temperature are studied
The extensive concern of person.In recent years, it is quickly grown by the two-dimentional c-based nanomaterial of representative of graphene, becomes the research of material circle
Hot spot.The conductivity at room temperature and fast carrier mobility that graphene has provide newly to develop the gas sensitive of working and room temperature
Thinking.Research finds grapheme material really and may be implemented room temperature detection gas, but the transducer sensitivity made it is lower,
It is slow to respond regeneration rate.Recently, grapheme modified using the excellent metal oxide nanoparticles of sensitive property, utilize metal oxygen
Compound surface oxygen functional group abundant, sensitivity and the response that graphene-based gas sensor can be further improved are extensive
Complex-velocity rate.By the structure of regulation metal oxide nanoparticles, the synergistic effect of metal oxide and graphene is given full play to,
It is expected to realize highly sensitive gas detection at room temperature.Graphene-based room temperature air sensor is developed as sensor field research
One of important directions develop very fast.
Summary of the invention
There is high sensitivity NO at room temperature the object of the present invention is to provide a kind of2Response characteristic based on be rich in Lacking oxygen
The resistor-type NO of the grapheme modified composite material of stannic oxide2Sensor, preparation method and its detection NO2In application.
It is of the present invention a kind of based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2It passes
Sensor deposits carbon interdigital electrode, the thickness of electrode in potsherd substrate surface using screen printing technique using potsherd as substrate
It is 1~2 μm, the logarithm of electrode is 4~6 pairs, and the width of each electrode is 50~100 μm；It is connected with and draws in carbon interdigital electrode
Line is coated with gas-sensitive film in potsherd substrate and carbon interdigital electrode surface, which is rich in Lacking oxygen
The grapheme modified composite material of stannic oxide, film with a thickness of 10~50 μm；Before and after gas-sensitive film contact measured gas
Its resistance can change, using electrochemical analyser (CHI, 660D, Shanghai Chen Hua Instrument Ltd.) to carbon electrode both ends
Apply 1V voltage, by the variation of electric current between measurement carbon interdigital electrode, the sensitivity of sensor, the calculating of sensitivity can be obtained
Method is the changing value of carbon electrode electric current in air and object gas divided by the aerial current value of carbon electrode.The richness
The grapheme modified composite material of oxygen-containing vacancy stannic oxide is formed, matter by graphene and stannic oxide mixing (area load)
Amount is than being 1:3.6~12；Using the distribution of oxygen element in X-ray photoelectron spectroscopic analysis composite material, it is found that composite material contains
There is Lacking oxygen abundant, the content of Lacking oxygen is 30%~50% in the occupation ratio of whole oxygen elements.
It is of the present invention a kind of based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2It passes
The preparation method of sensor, its step are as follows:
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 1~2 μm, and the logarithm of electrode is 4~6 pairs, and the width of each electrode is 50~100 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL~5mg/mL, by body
Product is the above-mentioned solution of 30mL~40mL hydro-thermal reaction 12~24 hours under the conditions of 160~180 DEG C, and redox graphene is made
Solution；
(4) four chlorinations of 0.012g~0.24g are added in the redox graphene solution then prepared to step (3)
Tin, ultrasonic disperse make its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:1.5~5:250
~12500；By above-mentioned solution hydro-thermal reaction 12~24 hours under the conditions of 160~180 DEG C, it is made and is rich in Lacking oxygen stannic oxide
The centrifuge separation of composite material solution, washing and drying are obtained oxygen-containing vacancy stannic oxide by grapheme modified composite material solution
The mass ratio of grapheme modified composite material, graphene and stannic oxide is 1:3.6~12；Composite material oxygen rich in is empty
Position, the content of Lacking oxygen are 30%~50%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, it is compound
The concentration of material is 1~10mg/mL；The solution is coated with the potsherd substrate with carbon interdigital electrode that step (2) obtains
Then surface is heat-treated 1~4 hour at 80~130 DEG C, obtained sensitive thin film with a thickness of 10~50 μm, thus be made
Based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor.
Gas sensor prepared by the present invention is used for NO2Room temperature response, NO2Concentration be not more than 20ppm, preferably not
Less than 1ppm, sensitivity 16.94%.The minimum concentration that can detecte is 1ppm.(NO in patent2Detectable concentration be 1~
20ppm)。
The invention has the advantages that
1) interdigital electrode is prepared using screen printing technique, low in cost, structure is easy to regulate and control, homogeneity of product is high；Carbon
Sensitive membrane and interelectrode adhesive force can be improved in strong π-π effect between electrode and grapheme material, improves the stability of device.
2) the grapheme modified composite material of Lacking oxygen stannic oxide is rich in using wet chemistry method preparation, method is simple, is easy to
Operation, it is low in cost.And the experiment parameters such as the ratio of control reaction temperature, reaction time and pre-reaction material can be passed through
Realize the regulation of the performances such as composition, the structure of graphene-based composite material.
3) in composite material stannic oxide introducing, can further prevent the reunion of graphene sheet layer, effectively mention
The specific surface area of high composite material.
4) in composite material graphene introducing, the electric conductivity of sensitive material can be improved significantly, avoid usual dioxy
Change tin because room temperature resistance is excessively high, response sensitivity is extremely low and cannot achieve room temperature detection gas.
5) tin dioxide nano-particle modification is on the surface of graphene in composite material, by stannic oxide Adsorption
Point and Lacking oxygen abundant realize that the regulation of surface-active site promotes the sensitive property of sensor.
6) tin dioxide nano-particle is generated using wet chemistry method on the surface of graphene, can significantly improve stannic oxide
And the combination of carbon-based material improves the conductivity at room temperature of material, is advantageously implemented room temperature detection.The composite material solution of preparation can
It is easy to process to be formed a film in interdigital electrode using the methods of spin coating, it prepares gas sensor with can be convenient, solves tradition
Metal-oxide gas transducer need high temperature sintering, process complicated problem.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of gas sensor of the invention.Wherein: potsherd substrate 1, carbon interdigital electrode 2 and 3,
Gas-sensitive film 4, lead 5 and 6.
Fig. 2 is the X-ray diffraction spectrogram rich in the grapheme modified composite material of Lacking oxygen stannic oxide.
Fig. 3 is the transmission electron microscope photo rich in the grapheme modified composite material of Lacking oxygen stannic oxide.
Fig. 4 is the x-ray photoelectron spectroscopy rich in the grapheme modified composite material of Lacking oxygen stannic oxide.
Fig. 5 is rich in the grapheme modified composite material gas sensor of Lacking oxygen stannic oxide to 1ppm~20ppm NO2
Room temperature dynamic response recovery curve.
Fig. 6 is the selectivity rich in the grapheme modified composite material gas sensor of Lacking oxygen stannic oxide to gas with various
Histogram.
Fig. 7 is rich in the grapheme modified composite material gas sensor of Lacking oxygen stannic oxide at room temperature to 5ppm dioxy
Change the response recovery curve of nitrogen.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and examples.
Embodiment 1
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 1 μm, and the logarithm of electrode is 4 pairs, and the width of each electrode is 50 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is 30mL by volume that the concentration of graphene oxide water solution, which is 0.1mg/mL,
Redox graphene solution is made hydro-thermal reaction 12 hours under the conditions of 160 DEG C in above-mentioned solution；
(4) tin tetrachloride of 0.012g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:5:12500；By above-mentioned solution
The hydro-thermal reaction 24 hours under the conditions of 180 DEG C is made and is rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide, will answer
Condensation material solution centrifuge separation, washing and drying, obtain the grapheme modified composite material of oxygen-containing vacancy stannic oxide, graphene and
The mass ratio of stannic oxide is 1:12；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 30%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 1mg/mL；It will be above-mentioned molten
Liquid is coated with the potsherd substrate surface with carbon interdigital electrode of step (2), and the sensitive material of acquisition in 4 hours is heat-treated at 80 DEG C
Expect film, film with a thickness of 10 μm, be made based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistor-type
Gas sensor.
Embodiment 2
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 1 μm, and the logarithm of electrode is 4 pairs, and the width of each electrode is 50 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is 30mL by volume that the concentration of graphene oxide water solution, which is 0.5mg/mL,
Redox graphene solution is made hydro-thermal reaction 12 hours under the conditions of 160 DEG C in above-mentioned solution；
(4) tin tetrachloride of 0.024g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:2:150~2500；It will be above-mentioned
Solution is made hydro-thermal reaction 24 hours under the conditions of 180 DEG C and is rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide,
By the centrifuge separation of composite material solution, washing and drying, the grapheme modified composite material of oxygen-containing vacancy stannic oxide, graphite are obtained
The mass ratio of alkene and stannic oxide is 1:4.8；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 32%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 2.5mg/mL；It will be above-mentioned
Solution is coated with the potsherd substrate surface with carbon interdigital electrode of step (2), and the sensitivity of acquisition in 1 hour is heat-treated at 90 DEG C
Material film, film with a thickness of 20 μm, be made based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistance
Type gas sensor.
Embodiment 3
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 1 μm, and the logarithm of electrode is 5 pairs, and the width of each electrode is 70 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is on 30mL by volume that the concentration of graphene oxide water solution, which is 1mg/mL,
Solution is stated hydro-thermal reaction 18 hours under the conditions of 170 DEG C, redox graphene solution is made；
(4) tin tetrachloride of 0.048g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:2:470；Above-mentioned solution is existed
Under the conditions of 170 DEG C when hydro-thermal reaction 18, it is made and is rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide, by composite wood
Expect solution centrifuge separation, washing and drying, obtains the grapheme modified composite material of oxygen-containing vacancy stannic oxide, graphene and dioxy
The mass ratio for changing tin is 1:4.8；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 35%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 5mg/mL；It will be above-mentioned molten
Liquid is coated with the potsherd substrate surface with carbon interdigital electrode of step (2), and the sensitivity of acquisition in 2 hours is heat-treated at 100 DEG C
Material film, film with a thickness of 30 μm, be made based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistance
Type gas sensor.
Embodiment 4
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 2 μm, and the logarithm of electrode is 5 pairs, and the width of each electrode is 70 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is on 40mL by volume that the concentration of graphene oxide water solution, which is 2mg/mL,
Solution is stated hydro-thermal reaction 18 hours under the conditions of 170 DEG C, redox graphene solution is made；
(4) tin tetrachloride of 0.096g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is that 1:1.5:625 exists above-mentioned solution
Hydro-thermal reaction 18 hours under the conditions of 170 DEG C are made and are rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide, will be compound
Material solution centrifuge separation, washing and drying, obtain the grapheme modified composite material of oxygen-containing vacancy stannic oxide, graphene and two
The mass ratio of tin oxide is 1:3.6；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 40%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 5mg/mL；It will be above-mentioned molten
Liquid is coated with the potsherd substrate surface with carbon interdigital electrode of step (2), and the sensitivity of acquisition in 2 hours is heat-treated at 110 DEG C
Material film, film with a thickness of 40 μm, be made based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistance
Type gas sensor.
Embodiment 5
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 2 μm, and the logarithm of electrode is 6 pairs, and the width of each electrode is 100 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is 40mL by volume that the concentration of graphene oxide water solution, which is 2.5mg/mL,
Redox graphene solution is made hydro-thermal reaction 24 hours under the conditions of 180 DEG C in above-mentioned solution；
(4) tin tetrachloride of 0.12g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:1.5:500；By above-mentioned solution
The hydro-thermal reaction 12 hours under the conditions of 160 DEG C is made and is rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide, will answer
Condensation material solution centrifuge separation, washing and drying, obtain the grapheme modified composite material of oxygen-containing vacancy stannic oxide, graphene and
The mass ratio of stannic oxide is 1:3.6；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 45%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 7.5mg/mL；By upper 120
Be heat-treated 4 hours acquisition sensitive material films at DEG C, film with a thickness of 45 μm, be made based on being repaired rich in Lacking oxygen stannic oxide
Adorn the resistor-type gas sensor of graphene composite material.
Embodiment 6
(1) using potsherd as substrate, carbon interdigital electrode, the thickness of electrode are deposited on potsherd surface using screen printing technique
Degree is 2 μm, and the logarithm of electrode is 6 pairs, and the width of each electrode is 100 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, it is on 40mL by volume that the concentration of graphene oxide water solution, which is 5mg/mL,
Solution is stated hydro-thermal reaction 24 hours under the conditions of 180 DEG C, redox graphene solution is made；
(4) tin tetrachloride of 0.24g, ultrasound point are added in the redox graphene solution then prepared to step (3)
Dissipating makes its mixing sufficiently, and the quality amount ratio of redox graphene, tin tetrachloride and water is 1:1.5:250；By above-mentioned solution
The hydro-thermal reaction 12 hours under the conditions of 160 DEG C is made and is rich in the grapheme modified composite material solution of Lacking oxygen stannic oxide, will answer
The centrifuge separation of condensation material solution, washing and drying, obtain oxygen-containing vacancy stannic oxide/graphene composite material, graphene and two
The mass ratio of tin oxide is 1:3.6；Composite material Lacking oxygen rich in, the content of Lacking oxygen are 50%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, prepares
Aqueous solution rich in the grapheme modified composite material of Lacking oxygen stannic oxide, the concentration of composite material are 10mg/mL；It will be above-mentioned molten
Liquid is coated with the potsherd substrate surface with carbon interdigital electrode of step (2), and the sensitivity of acquisition in 4 hours is heat-treated at 130 DEG C
Material film, film with a thickness of 50 μm, be made based on be rich in the grapheme modified composite material of Lacking oxygen stannic oxide resistance
Type gas sensor.
X-ray diffraction spectrogram such as Fig. 2 rich in the grapheme modified composite material of Lacking oxygen stannic oxide prepared by embodiment 1
Shown, as seen from Figure 2, composite material has the diffraction maximum for typically belonging to stannic oxide, illustrates that composite material contains
By stannic oxide.
Transmission electron microscope photo such as Fig. 3 rich in the grapheme modified composite material of Lacking oxygen stannic oxide prepared by embodiment 1
It is shown.As seen from Figure 3, tin dioxide nano-particle is uniformly dispersed in the sheet surfaces of graphene.
X-ray photoelectron spectroscopy rich in the grapheme modified composite material of Lacking oxygen stannic oxide prepared by embodiment 1 is such as
Shown in Fig. 4, as seen from Figure 4, a large amount of vacancy oxygen is contained in composite material, the content of vacancy oxygen is in total oxygen element content
30%.
Embodiment 1 prepare based on rich in the grapheme modified composite material gas sensor of Lacking oxygen stannic oxide in room temperature
Under Fig. 5 is shown in the response recovery curve of various concentration nitrogen dioxide.As can be seen that the graphene-based gas sensor of preparation is not to
With concentration nitrogen dioxide have very high, cracking response, the response time less than 1 minute, and sensor have well may be used
Inverse property.
Embodiment 1 prepare based on rich in the grapheme modified composite material of Lacking oxygen stannic oxide gas sensor in room
Fig. 6 is selectively shown in the response of 5ppm gas with various under temperature.As can be seen that sensor is to NO2Show excellent selectivity.
Embodiment 2 prepare based on rich in the grapheme modified composite material gas sensor of Lacking oxygen stannic oxide in room temperature
Under Fig. 7 is shown in the response recovery curve of 5ppm nitrogen dioxide.As can be seen that the graphene-based gas sensor of preparation is to 5ppm bis-
Nitrogen oxide has good response recovery characteristics.
Claims (3)
1. a kind of based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2The preparation method of sensor,
Its step are as follows:
(1) using potsherd as substrate, using screen printing technique potsherd surface deposit carbon interdigital electrode, electrode with a thickness of
1~2 μm, the logarithm of electrode is 4~6 pairs, and the width of each electrode is 50~100 μm；
(2) successively it is cleaned by ultrasonic the potsherd substrate that surface is prepared with carbon interdigital electrode with ethyl alcohol, water, dries；
(3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL~5mg/mL, is by volume
It is molten that redox graphene is made hydro-thermal reaction 12~24 hours under the conditions of 160~180 DEG C in the above-mentioned solution of 30mL~40mL
Liquid；
(4) tin tetrachloride of 0.012g~0.24g is added in the redox graphene solution then prepared to step (3), surpasses
Sound dispersion makes its mixing sufficiently, the quality amount ratio of redox graphene, tin tetrachloride and water be 1:1.5~5:250~
12500；By above-mentioned solution hydro-thermal reaction 12~24 hours under the conditions of 160~180 DEG C, it is made and is repaired rich in Lacking oxygen stannic oxide
Graphene composite material solution is adornd, by the centrifuge separation of composite material solution, washing and drying, oxygen-containing vacancy stannic oxide is obtained and repairs
The mass ratio of decorations graphene composite material, graphene and stannic oxide is 1:3.6~12；Composite material oxygen rich in is empty
Position, the content of Lacking oxygen are 30%~50%；
(5) being distributed in water rich in the grapheme modified composite material of Lacking oxygen stannic oxide by step (4) preparation, composite material
Concentration be 1~10mg/mL；The solution is coated with the potsherd substrate surface with carbon interdigital electrode that step (2) obtains,
Then be heat-treated 1~4 hour at 80~130 DEG C, obtained sensitive thin film with a thickness of 10~50 μm, thus be made based on richness
The resistor-type NO of the grapheme modified composite material of oxygen-containing vacancy stannic oxide2Sensor.
2. a kind of based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor, feature exist
In: it is to be prepared by method described in claim 1.
3. as claimed in claim 2 a kind of based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2It passes
Sensor is in detection NO2In application.
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| CN110243881A (en) * | 2019-07-16 | 2019-09-17 | 东北大学 | One kind being based on rGO-SnO2The NO of nanocomposite2Gas sensor and preparation method thereof |
| CN111024777A (en) * | 2019-12-25 | 2020-04-17 | 广州钰芯传感科技有限公司 | Sensor for modifying tin oxide, preparation method thereof and application of sensor 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 |
| CN113325041A (en) * | 2021-05-31 | 2021-08-31 | 吉林大学 | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof |
| CN114014313A (en) * | 2022-01-06 | 2022-02-08 | 河北化工医药职业技术学院 | Graphene-based gas-sensitive material and preparation method thereof |
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