CN110068597A - A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof - Google Patents

A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof Download PDF

Info

Publication number
CN110068597A
CN110068597A CN201910368006.7A CN201910368006A CN110068597A CN 110068597 A CN110068597 A CN 110068597A CN 201910368006 A CN201910368006 A CN 201910368006A CN 110068597 A CN110068597 A CN 110068597A
Authority
CN
China
Prior art keywords
zinc oxide
sensor
nano material
type
ceramic tube
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.)
Pending
Application number
CN201910368006.7A
Other languages
Chinese (zh)
Inventor
刘森
张彤
费腾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201910368006.7A priority Critical patent/CN110068597A/en
Publication of CN110068597A publication Critical patent/CN110068597A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/505—Tin oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • 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

Abstract

A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof belongs to gas sensor technical field.Sensor is tubular structure, by Al2O3Ceramic tube substrate is coated in Al2O3The parallel and separate cyclic annular Au electrode of two of ceramic tube outer substrate surface is coated in Al2O3Stannic oxide modification zinc oxide nano material gas-sensitive film on ceramic tube outer surface and ring-type Au electrode, across Al2O3The nichrome heating coil of ceramic tube inside forms.Surface-functionalized tin oxide modification zinc oxide nano material is to NO2With excellent gas-sensitive property, including high sensitivity and fast response regeneration rate, solve the problems, such as that the usual sensitive property of pure state zinc oxide gas sensor is poor.The present invention can realize the regulation of the performances such as composition, the structure for showing functionalization zinc oxide material by experiment parameters such as the ratios of control reaction temperature, reaction time and pre-reaction material, to improve the performance of sensor.

Description

A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and Its production method
Technical field
The invention belongs to gas sensor technical fields, and in particular to a kind of functionalization oxidation with air-sensitive response characteristic Zinc resistor-type NO2Sensor and preparation method thereof, more particularly to a kind of based on stannic oxide modification zinc oxide nano material Resistor-type NO2Sensor and preparation method thereof.
Background technique
With the fast development of industrial or agricultural and transportation, problem of environmental pollution is more and more prominent.In particular with vapour The sustainable growth of vehicle ownership, NO in atmospheric environment2Concentration it is higher and higher, not only the respiratory system of organism is generated serious Harm, serious destruction also is brought to the living environment of the mankind.To the NO in environment2Carrying out accurate, continuous detection becomes Urgent problem to be solved, this just provides wide space for the application of gas sensor.Gas sensor is a kind of important Chemical sensor has a wide range of applications in the fields such as industrial and agricultural production, process control, environmental monitoring and protection and anti-terrorism.It grinds Fixture has the advantages that high sensitivity, low cost, low-power consumption, the high performance gas sensor minimized become scientific research field and industry The research hotspot on boundary.
Currently, researchers' design is prepared for the NO based on different micro Nano materials2Sensor.With stannic oxide, oxidation Zinc is that the conductor oxidate of representative becomes the most widely used a kind of sensitive material, have prepare it is convenient, low in cost, The advantages that from a wealth of sources.Although detection NO may be implemented in conductor oxidate2, but need the microcosmic knot of carefully control material Structure leads to synthesis condition complexity, sample low yield, and stability is poor, is affected by humidity, and selectivity is not ideal enough etc..It leads Room temperature detection NO may be implemented in electric copolymer material2, but sensitivity is lower, regeneration rate is very slow；Using graphene as representative New Two Dimensional nano material equally may be implemented room temperature detection NO2, low sensitivity and slow response regeneration rate are still Limit its widely applied bottleneck.NO based on oxygen ion conductor2There is sensor high sensitivity and fast response to restore speed Rate, high operating temperature make it difficult to apply in the other field except gas tail gas monitors.
Although conductor oxidate NO2The detection temperature of sensor is higher, but high sensitivity and fast response restore Rate becomes exploitation high-performance NO at present2The first choice of sensor.Although zinc oxide is as a kind of typical n-type semiconductor material Material is widely used in and constructs different types of gas sensor, but the surface-active number of sites amount of pure state zinc oxide compared with It is few, to NO2Sensitive property it is poor, especially organic volatile seriously interferes its sensitive property.Research is found to zinc oxide Surface carry out moditied processing, can regulate and control its surface microstructure, promote surface-active number of sites amount, and then lift gas is quick Perceptual energy.Develop based on surface-functionalized conductor oxidate gas sensor become sensor field research important directions it One, develop very fast.
Summary of the invention
The object of the present invention is to provide one kind to have high sensitivity NO2Response characteristic based on stannic oxide modification zinc oxide The resistor-type NO of nano material2Sensor and preparation method thereof.
A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material of the present invention2Sensor, for pipe Formula structure, by Al2O3Ceramic tube substrate is coated in Al2O3Two parallel and separate ring-types of ceramic tube outer substrate surface Au electrode is coated in Al2O3Gas-sensitive film on ceramic tube outer surface and ring-type Au electrode, across Al2O3Ceramic tube inside Nichrome heating coil composition；It is characterized by: the gas-sensitive film is that surface-functionalized stannic oxide modifies oxygen Change zinc nano material, be prepared by following steps,
(1) under vacuum conditions by 1~5g Zinc oxide powder, 60~80 DEG C heat treatment 12~for 24 hours；
(2) Zinc oxide powder obtained in step (1) is added in toluene solution, the volume of toluene is 50~70mL, is surpassed Sound makes it be uniformly dispersed；Addition 0.2~1.0g dimethyltin chloride in solution is stated then up, and 0.5~1h is stirred at room temperature, obtains To dimethyltin chloride and zinc oxide mixed solution；
(3) 4~6mL triethylamine is added in the dimethyltin chloride and zinc oxide mixed solution that step (2) obtains, Continue that 2~4h is stirred at room temperature；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, obtain Organotin modification zinc oxide Material；
(4) zinc oxide material by the Organotin modification that step (3) obtains calcines 2~4h at 500~600 DEG C, obtains To tin oxide modification zinc oxide nano material powder；
Al2O3The length of ceramic tube is 4~4.5mm, and outer diameter is 1.2~1.5mm, and internal diameter is 0.8~1.0mm；Nichrome Heating coil provides operating temperature for sensor, and the resistance value of heating coil is 30~40 Ω；The width of cyclic annular Au electrode be 0.7~ 0.9mm, the spacing of two electrodes are 1.7~1.9mm.Gas-sensitive film with a thickness of 100~200 μm；Gas-sensitive film Before and after contact measured gas, resistance can change, and by measuring the variation of two ring-type Au electrode resistances, can be passed The sensitivity of sensor.The calculation method of sensitivity be cyclic annular gold electrode in air resistance value divided by its electricity in object gas Resistance value.
A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material of the present invention2The preparation of sensor Method, its step are as follows:
(1) ratio of tin oxide modification zinc oxide nano material powder and deionized water 2~4:1 in mass ratio are mixed, And it is ground into pasty slurry, which is coated to the Al that outer surface has two parallel and separate cyclic annular gold electrodes2O3 Ceramic pipe surface；
(2) device for obtaining step (1) toasts 20~30 minutes under infrared lamp, will be electric after sensitive material is dry The nichrome heating coil that resistance value is 30~40 Ω passes through Al2O3Ceramic tube as heater strip, according to heater-type gas sensor into Row welding and encapsulation；
(3) device for obtaining step (2) aging process 10~20 hours at 300~350 DEG C, to obtain based on oxygen Change tin modification zinc oxide nano material resistor-type NO2Sensor.
The invention has the advantages that
1) surface-functionalized processing is carried out to zinc oxide using Organometallic Chemistry method, this method is simple, efficient, yield Height, suitable for mass production.
2) the surface-functionalized tin oxide modification zinc oxide nano material prepared by is to NO2It is special with excellent air-sensitive Property, including high sensitivity and fast response regeneration rate, solve the usual sensitive property of pure state zinc oxide gas sensor compared with The problem of difference.
3) NO based on function of surface zinc oxide prepared by the present invention2Sensor manufacturing process is simple, low in cost, It is small in size, it is suitble to industrial batch production.
4) preparation method of surface-functionalized nano zinc oxide material is easy to regulate and control the surface of zinc oxide material in the present invention Micro-structure can show function by the experiment parameters realization such as ratio of control reaction temperature, reaction time and pre-reaction material The regulation of the performances such as composition, the structure of energy zinc oxide material.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of gas sensor of the invention.
Each section title are as follows: Al2O3Ceramic tube 1 passes through Al2O3The nichrome heater strip 2 of ceramic tube 1, in Al2O3Ceramics Two parallel and cricoid gold electrodes 3 of 1 surface of pipe coating, in cyclic annular gold electrode and Al2O3The gas of ceramic pipe surface coating is quick Feel film 4 (surface-functionalized zinc oxide material of the present invention).
Fig. 2 is the stereoscan photograph of the different amplification of tin oxide modification zinc oxide nano material.
Fig. 3 is the X-ray color map of tin oxide modification zinc oxide nano material.
Fig. 4 is that the sensor based on tin oxide modification zinc oxide nano material in embodiment 1 is right at a temperature of different operating 0.5ppm NO2Response with operating temperature variation relation curve.
Fig. 5 be sensor based on tin oxide modification zinc oxide nano material in embodiment 1 under the conditions of 240 DEG C to difference The response curve of gas.
Fig. 6 is that the sensor based on tin oxide modification zinc oxide nano material in embodiment 2 is right under the conditions of 230 DEG C 0.5ppm NO2Response recovery curve.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and examples.
Embodiment 1
(1) under vacuum conditions by 1g Zinc oxide powder, 60 DEG C of heat treatment 12h；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 50mL, and ultrasound keeps its dispersion equal It is even；Addition 0.2g dimethyltin chloride in solution is stated then up, and 0.5h is stirred at room temperature, obtains dimethyltin chloride and oxygen Change zinc mixed solution；
(3) 4mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 2h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 500 DEG C of temperature lower calcination 2h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 2:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.8mm；The width of annular electrode For 0.7mm, the spacing of two electrodes is 1.7mm.It toasts 30 minutes under infrared lamp, obtains in ceramic pipe surface based on surface work Can zinc oxide sensitive membrane, sensitive membrane with a thickness of 100 μm；Then the nichrome that resistance value is 40 Ω is worn compared with heat coil Cross Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 10 at 300 DEG C Hour, the aging process to gas sensor is completed, to obtain based on tin oxide modification zinc oxide nano material resistor-type NO2 Sensor.
Embodiment 2
(1) under vacuum conditions by 2g Zinc oxide powder, 60 DEG C of heat treatment 12h；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 50mL, and ultrasound keeps its dispersion equal It is even；Addition 0.4g dimethyltin chloride in solution is stated then up, and 0.5h is stirred at room temperature, obtains dimethyltin chloride and oxygen Change zinc mixed solution；
(3) 4mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 2h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 500 DEG C of temperature lower calcination 2h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 2:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.8mm；The width of annular electrode For 0.7mm, the spacing of two electrodes is 1.7mm.It toasts 30 minutes under infrared lamp, obtains in ceramic pipe surface based on surface work Can zinc oxide sensitive membrane, sensitive membrane with a thickness of 100 μm；Then the nichrome that resistance value is 40 Ω is worn compared with heat coil Cross Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 15 at 300 DEG C Hour, the aging process to gas sensor is completed, to obtain based on tin oxide modification zinc oxide nano material resistor-type NO2 Sensor.
Embodiment 3
(1) under vacuum conditions by 3g Zinc oxide powder, 70 DEG C of heat treatment 18h；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 60mL, and ultrasound keeps its dispersion equal It is even；Addition 0.5g dimethyltin chloride in solution is stated then up, and 0.5h is stirred at room temperature, obtains dimethyltin chloride and oxygen Change zinc mixed solution；
(3) 5mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 3h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 550 DEG C of temperature lower calcination 3h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 3:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4mm, outer diameter 1.2mm, internal diameter 0.9mm；The width of annular electrode For 0.8mm, the spacing of two electrodes is 1.8mm.It toasts 30 minutes under infrared lamp, obtains in ceramic pipe surface based on surface work Can zinc oxide sensitive membrane, sensitive membrane with a thickness of 150 μm；Then the nichrome that resistance value is 40 Ω is worn compared with heat coil Cross Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 20 at 300 DEG C Hour, the aging process to gas sensor is completed, to obtain based on tin oxide modification zinc oxide nano material resistor-type NO2 Sensor.
Embodiment 4
(1) under vacuum conditions by 4g Zinc oxide powder, 70 DEG C of heat treatment 18h；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 60mL, and ultrasound keeps its dispersion equal It is even；Addition 0.6g dimethyltin chloride in solution is stated then up, 1h is stirred at room temperature, and obtains dimethyltin chloride and oxidation Zinc mixed solution；
(3) 5mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 3h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 550 DEG C of temperature lower calcination 3h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 3:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4.5mm, outer diameter 1.5mm, internal diameter 0.9mm；The width of annular electrode Degree is 0.8mm, and the spacing of two electrodes is 1.8mm.It toasts 20 minutes under infrared lamp, obtains in ceramic pipe surface based on surface The sensitive membrane of function zinc oxide, sensitive membrane with a thickness of 150 μm；Then by resistance value be 30 Ω nichrome compared with heat coil Across Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 10 at 350 DEG C Hour, the aging process to gas sensor is completed, to obtain based on tin oxide modification zinc oxide nano material resistor-type NO2 Sensor.
Embodiment 5
(1) under vacuum conditions by 5g Zinc oxide powder, it is heat-treated for 24 hours for 80 DEG C；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 70mL, and ultrasound keeps its dispersion equal It is even；Addition 0.8g dimethyltin chloride in solution is stated then up, 1h is stirred at room temperature, and obtains dimethyltin chloride and oxidation Zinc mixed solution；
(3) 6mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 4h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 600 DEG C of temperature lower calcination 4h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 4:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4.5mm, outer diameter 1.5mm, internal diameter 1.0mm；The width of annular electrode Degree is 0.9mm, and the spacing of two electrodes is 1.9mm.It toasts 20 minutes under infrared lamp, obtains in ceramic pipe surface based on surface The sensitive membrane of function zinc oxide, sensitive membrane with a thickness of 200 μm；Then by resistance value be 30 Ω nichrome compared with heat coil Across Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 15 at 350 DEG C Hour, the aging process to gas sensor is completed, to obtain based on tin oxide modification zinc oxide nano material resistor-type NO2 Sensor.
Embodiment 6
(1) under vacuum conditions by 5g Zinc oxide powder, it is heat-treated for 24 hours for 80 DEG C；
(2) Zinc oxide powder in (1) is added in toluene solution, the volume of toluene is 70mL, and ultrasound keeps its dispersion equal It is even；Addition 1.0g dimethyltin chloride in solution is stated then up, 1h is stirred at room temperature, and obtains dimethyltin chloride and oxidation Zinc mixed solution；
(3) 6mL triethylamine is added to dimethyltin chloride and zinc oxide mixed solution in (2), continues to be stirred at room temperature 4h；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, the zinc oxide material of acquisition Organotin modification；
(4) zinc oxide material by the Organotin modification prepared in (3) obtains surface in 600 DEG C of temperature lower calcination 4h Functionalization zinc oxide material；
(5) the surface-functionalized Zinc oxide powder of step (4) preparation and the deionized water ratio of 4:1 in mass ratio is mixed It closes, and is ground into pasty slurry, which is coated to outer surface parallel with two, ring-type and gold electrode separate Al2O3Ceramic pipe surface, Al203The length of ceramic tube is 4.5mm, outer diameter 1.5mm, internal diameter 1.0mm；The width of annular electrode Degree is 0.9mm, and the spacing of two electrodes is 1.9mm.It toasts 20 minutes under infrared lamp, obtains in ceramic pipe surface based on surface The sensitive membrane of function zinc oxide, sensitive membrane with a thickness of 200 μm；Then by resistance value be 30 Ω nichrome compared with heat coil Across Al2O3Ceramic tube is finally welded and is encapsulated according to heater-type gas sensor as heater strip；
(6) NO based on function of surface zinc oxide for obtaining step (5)2Gas sensor is heat-treated 20 at 350 DEG C Hour, it completes to gas sensor
The stereoscan photograph of tin oxide modification zinc oxide nano material prepared by embodiment 1 is as shown in Fig. 2, can by Fig. 2 To find out, composite material has typical lamellar structure, each lamella has small nanoparticle to constitute, between particle and particle With the presence of gap.
The X-ray electronic diffraction map of tin oxide modification zinc oxide nano material prepared by embodiment 1 is shown in Fig. 3.It can see Out, the zinc oxide material of preparation provides a series of diffraction maximums, these diffraction maximums belong to zincblende zincite crystal, illustrates success Ground is prepared for zinc oxide material.
Tin oxide modification zinc oxide nano material prepared by embodiment 1 is at a temperature of different operating to 0.5ppm NO2Spirit Sensitivity is shown in Fig. 3 between the variation relation curve of operating temperature.As operating temperature is increased to 220 DEG C by 200 DEG C, element it is sensitive Degree gradually rises.With the further raising of operating temperature, the sensitivity of element is gradually reduced, and element is at 220 DEG C to 0.5ppm NO2Sensitivity be 32.
Gas sensor based on tin oxide modification zinc oxide nano material prepared by embodiment 1 is at room temperature for difference The selective response of gas is shown in Fig. 5.As can be seen that sensor is to NO2With good response, the surface sensor has good Good selectivity.
Gas sensor based on tin oxide modification zinc oxide nano material prepared by embodiment 2 is at 230 DEG C to 0.5 pair 0.5ppm NO2Response recovery curve it is as shown in Figure 6.It can be seen that show high sensitivity, response regeneration rate fast etc. for element Advantage.

Claims (4)

1. a kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor is tubular structure, by Al2O3Pottery Porcelain tube substrate is coated in Al2O3The parallel and separate cyclic annular Au electrode of two of ceramic tube outer substrate surface is coated in Al2O3Gas-sensitive film on ceramic tube outer surface and ring-type Au electrode, across Al2O3The nichrome of ceramic tube inside adds Heat coil composition；It is characterized by: the gas-sensitive film is surface-functionalized stannic oxide modification zinc oxide nano material, It is prepared by following steps,
(1) under vacuum conditions by 1~5g Zinc oxide powder, 60~80 DEG C heat treatment 12~for 24 hours；
(2) Zinc oxide powder obtained in step (1) is added in toluene solution, the volume of toluene is 50~70mL, and ultrasound makes It is uniformly dispersed；Addition 0.2~1.0g dimethyltin chloride in solution is stated then up, and 0.5~1h is stirred at room temperature, obtains two Methyl dichloro tin and zinc oxide mixed solution；
(3) 4~6mL triethylamine is added in the dimethyltin chloride and zinc oxide mixed solution that step (2) obtains, is continued 2~4h is stirred at room temperature；Above-mentioned solution is centrifuged, ethyl alcohol is washed, is dried, obtain Organotin modification zinc oxide material Material；
(4) zinc oxide material by the Organotin modification that step (3) obtains calcines 2~4h at 500~600 DEG C, obtains oxygen Change tin modification zinc oxide nano material powder.
2. a kind of resistor-type NO based on stannic oxide modification zinc oxide nano material as described in claim 12Sensor, Be characterized in that: gas-sensitive film with a thickness of 100~200 μm.
3. a kind of resistor-type NO based on stannic oxide modification zinc oxide nano material as described in claim 12Sensor, It is characterized in that: Al2O3The length of ceramic tube is 4~4.5mm, and outer diameter is 1.2~1.5mm, and internal diameter is 0.8~1.0mm；Nickel chromium triangle closes The resistance value of golden heating coil is 30~40 Ω；The width of cyclic annular Au electrode is 0.7~0.9mm, the spacing of two electrodes is 1.7~ 1.9mm。
4. a kind of resistor-type NO based on stannic oxide modification zinc oxide nano material described in claim 12The preparation of sensor Method, its step are as follows:
(1) ratio of tin oxide modification zinc oxide nano material powder and deionized water 2~4:1 in mass ratio are mixed, and ground Pasty slurry is worn into, which is coated to the Al that outer surface has two parallel and separate cyclic annular gold electrodes2O3Ceramics Pipe surface；
(2) device for obtaining step (1) toasts 20~30 minutes under infrared lamp, after sensitive material is dry, by resistance value Al is passed through for the nichrome heating coil of 30~40 Ω2O3Ceramic tube is welded as heater strip according to heater-type gas sensor It connects and encapsulates；
(3) device for obtaining step (2) aging process 10~20 hours at 300~350 DEG C, to obtain based on tin oxide Modification zinc oxide nano material resistor-type NO2Sensor.
CN201910368006.7A 2019-05-05 2019-05-05 A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof Pending CN110068597A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910368006.7A CN110068597A (en) 2019-05-05 2019-05-05 A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910368006.7A CN110068597A (en) 2019-05-05 2019-05-05 A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110068597A true CN110068597A (en) 2019-07-30

Family

ID=67369937

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910368006.7A Pending CN110068597A (en) 2019-05-05 2019-05-05 A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110068597A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111198208A (en) * 2020-01-14 2020-05-26 杭州电子科技大学 Polypeptide-regulated zinc oxide-prepared NO2Method for gas sensor
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
CN113916945A (en) * 2021-10-06 2022-01-11 吉林大学 SnO (stannic oxide) -based2Gas sensor of-ZnO porous graded structure sensitive material, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106053556A (en) * 2016-05-13 2016-10-26 吉林大学 Ethanol gas sensor based on ZnO/SnO2 heterostructure composite material and preparation method thereof
CN108828021A (en) * 2018-05-03 2018-11-16 吉林大学 Based on branching SnO2The alcohol gas sensor and preparation method thereof of/ZnO heterojunction structure sensitive material
CN108896622A (en) * 2018-05-09 2018-11-27 广东美的制冷设备有限公司 The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106053556A (en) * 2016-05-13 2016-10-26 吉林大学 Ethanol gas sensor based on ZnO/SnO2 heterostructure composite material and preparation method thereof
CN108828021A (en) * 2018-05-03 2018-11-16 吉林大学 Based on branching SnO2The alcohol gas sensor and preparation method thereof of/ZnO heterojunction structure sensitive material
CN108896622A (en) * 2018-05-09 2018-11-27 广东美的制冷设备有限公司 The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SEN LIU, ET. AL: "Oxygen vacancy modulation of commercial SnO2 by an organometallic chemistry-assisted strategy for boosting acetone sensing performances", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
ZHIYONG ZHANG, ET. AL: "Novel SnO2 @ZnO hierarchical nanostructures for highly sensitive and selective NO2 gas sensing", 《SENSORS AND ACTUATORS B: CHEMICAL》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111198208A (en) * 2020-01-14 2020-05-26 杭州电子科技大学 Polypeptide-regulated zinc oxide-prepared NO2Method for gas sensor
CN111198208B (en) * 2020-01-14 2022-07-01 杭州电子科技大学 Polypeptide-regulated zinc oxide-prepared NO2Method for gas sensor
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
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
CN113916945A (en) * 2021-10-06 2022-01-11 吉林大学 SnO (stannic oxide) -based2Gas sensor of-ZnO porous graded structure sensitive material, preparation method and application thereof

Similar Documents

Publication Publication Date Title
Wang et al. Self-assembled and Pd decorated Zn2SnO4/ZnO wire-sheet shape nano-heterostructures networks hydrogen gas sensors
Choi et al. Synthesis and gas sensing performance of ZnO–SnO2 nanofiber–nanowire stem-branch heterostructure
CN110068597A (en) A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof
Wan et al. Fabrication and ethanol sensing characteristics of ZnO nanowire gas sensors
CN106124573B (en) A kind of acetone gas sensor and preparation method thereof based on NiO/ZnO heterojunction structure hollow sphere sensitive material
Jun et al. Necked ZnO nanoparticle-based NO2 sensors with high and fast response
Ho Gas sensor with nanostructured oxide semiconductor materials
CN108254416A (en) Meso-hole structure In is supported based on Au2O3The NO of nano sensitive material2Sensor, preparation method and applications
CN105548275A (en) Acetone sensor based on NiO/ZnO heterostructure nanoflower sensitive material and preparation method of acetone sensor
Huang et al. Fabrication of rigid and flexible SrGe 4 O 9 nanotube-based sensors for room-temperature ammonia detection
CN102012386A (en) Preparation method of nitric oxide gas sensor element based on pseudodirected tungsten trioxide nano tape
CN111060560B (en) Ru-WO3 nano material and preparation method and application thereof
Singh et al. Highly sensitive nitric oxide gas sensor based on ZnO-nanorods vertical resistor operated at room temperature
Yu et al. Highly sensitive and low detection limit of ethanol gas sensor based on CeO2 nanodot-decorated ZnSnO3 hollow microspheres
CN109839408B (en) Ammonia gas sensor with nano composite material as sensing film
CN113189153A (en) Ethanol sensor based on ZnO porous nanosheet microsphere sensitive material, preparation method and application thereof
Min et al. Fabrication of highly sensitive and selective acetone sensor using (p)-Co3O4 nanoparticle-decorated (n)-ZnO nanowires
CN107966480A (en) One kind is based on graphene coated α-Fe2O3The room temperature NO of compound2Sensor and preparation method thereof
CN105136869B (en) Polyaniline/ferric oxide nano composite resistance type material sensors and preparation method thereof
CN107884446B (en) Ethanol gas sensor based on multi-element metal oxide sensitive material
CN105424759A (en) Preparation method of zinc oxide nanotube array gas sensitive sensor
CN113049646A (en) Based on Cu7S4Hydrogen sulfide sensor made of-CuO graded structure micro-flower sensitive material and preparation method thereof
Sinha et al. Temperature dependent selectivity switching from methanol to formaldehyde using ZnO nanorod based chemi-resistive sensor
CN110687185A (en) Based on SnO2@Fe2O3Low-power-consumption acetone gas sensor of nano heterostructure sensitive material and preparation method thereof
CN109292734A (en) A kind of room temperature flexible gas sensor and preparation method thereof based on polycrystalline micro wire grain boundary effect

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20190730

RJ01 Rejection of invention patent application after publication