CN108663417B - One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive - Google Patents
One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
- C01G30/005—Oxides
Abstract
The invention discloses one kind to be directed to low concentration of NO2Novel I n with excellent air-sensitive performance2O3/Sb2O3Composite hollow nanotube gas sensitive, gas sensor and preparation method thereof and application.The novel I n2O3/Sb2O3Composite semiconductor gas sensitive is mutually made of by certain mol proportion matrix phase and modification, and the matrix is the In of porous structure2O3Modification phase is distributed in hollow nanotube, matrix surface and porous structure duct, the modification is mutually Sb2O3.The present invention also provides the preparation method of tandem semiconductor gas sensitive, the production method of gas sensor and its air-sensitive performances.Novel I n of the invention2O3/Sb2O3Composite hollow nanotube gas sensitive is to low concentration of NO2Gas has the characteristics that high sensitivity and selective, low operating temperature and response and recovery time are fast.Preparation method of the invention is simple, and technological parameter is easy to control, and operation is easy and at low cost.
Description
Technical field
The present invention relates to a kind of Semiconductor gas sensors materials of compound structure for new residence, in particular to a kind of to be directed to low concentration of NO2
The indium oxide of gas/antimony oxide composite Nano hollow pipe gas sensitive, belongs to gas sensitive technical field.
Background technique
With increasingly developed, the living standards of the people continuous improvement of science and technology, industrial waste gas and life exhaust gas (such as NO2、
SO2、 H2S, CO etc.) discharge amount it is also increasing, the environmental pollution (such as haze, acid rain, greenhouse effects) that people are faced
The problem of also get worse.Therefore, the discharge of effective monitoring management polluted gas becomes current essential governing measure.By
The gas detection technology that gas sensitive material is led is by worldwide great attention.NO2Gas is as industrial waste gas and life
Typical polluted gas in exhaust gas living, chemical activity with higher and stronger corrosivity, and can in air moisture or
Hydrocarbon reacts, and is the main source to form the secondary pollutions such as acid rain, photochemical fog and haze, seriously threatens
The health of people and the living environment lived.According to Industrial Hygiene Association of U.S. Government (ACGIH) and employment security with
The data of health control office (US) show that people allow to be exposed to NO2Threshold limit value in gas is 3ppm, wherein 1ppm's
NO2The time of exposure is no more than 15min in gas.Therefore, the gas sensing materials pair with highly sensitive selectivity are designed
Detect low concentration of NO2Gas is of great significance.
In2O3As typical N-type semiconductor material, NO is had been widely used in2The detection of gas.However, numerous studies
Show usually pure metal oxide gas sensitive to NO2The poor selectivity of gas, detectable concentration is limited and when detecting vulnerable to
The interference of other gases.Meanwhile temperature needed for work is excessively high, generally reaches several hundred degrees Celsius, to the power of instrument and equipment
It is required that high.In addition to this, exist to low concentration of NO2The response of gas is low, and sensitivity is weaker, and response and recovery capability are not
Foot, the disadvantages such as time length.Currently, in order to improve In2O3Gas sensitive is to low concentration of NO2The detection performance of gas is usually selected expensive
Metallic catalyst (such as Au, Ag, Pt) promotes NO2In the electron exchange of indium oxide material surface, it is improved to NO2Gas
Sensitivity.Although however noble metal use improve its air-sensitive performance, higher production cost limits indium oxide material
The practical application of material.Metal oxide semiconductor material due to its unique electronic structure, make its with indium oxide it is compound after, by
It is different in the two work function, heterojunction structure is formd at composite material two-phase interface.In material air-sensitive performance test process,
The electron transfer that exists for of heterojunction structure provides potential energy barrier, and the material resistance for increasing gas contact front and back becomes
Change, and then increases its sensitivity to gas.Therefore, metal oxide semiconductor material is mutually used to mention as potential modification
The air-sensitive performance of high-purity indium oxide reduces production cost, expands its application range and have a very important significance.But it selects
A kind of suitable metal oxide improves pure zirconia indium to low concentration of NO2The performance of gas is very crucial.
In design to low concentration of NO2In with good air-sensitive performance2O3Sill simultaneously, in addition to ingredient to be considered change
Other than brought electronic structure variation, the microscopic appearance and particle size of material can also generate the air-sensitive performance of material important
Influence.The study found that porous structure can provide transport channel abundant for the diffusion of gas on the surface of the material.In addition, big
Surface area provide more active positions for the absorption of gas on the surface of the material.These greatly improve the sensitivity of material
With response and recovery time.Therefore, it is provided in the present invention a kind of using MOFs as the side of precursor preparation porous metal oxide
Method, and propose a kind of pair of low concentration of NO2Novel I n with excellent air-sensitive performance2O3/Sb2O3Composite material.
Summary of the invention
To overcome pure zirconia indium to low concentration of NO2The deficiency that gas response is low, poor selectivity, operating temperature are high, this hair
It is bright that a kind of pair of low concentration of NO is provided2Gas has the novel I n of excellent air-sensitive performance2O3/Sb2O3Composite hollow nanotube air-sensitive material
Material and preparation method thereof.
To achieve the goals above, the present invention adopts the following technical scheme:
In order to improve pure zirconia indium to low concentration of NO2The air-sensitive performance of gas expands its application range and actual production, this
Invention provides a kind of Sb of novel low cost2O3Semiconductor and In2O3It is compound, it is improved by forming p-n heterojunction structure
To low concentration of NO2Sensitivity and selectivity.For this purpose, there is provided one kind to be directed to low concentration of NO for an object of the present invention2Gas
Novel I n2O3/Sb2O3Composite hollow nanotube gas sensitive, the gas sensitive is by metal oxide nanotubes and modifies it
On modification phase particle composition；Wherein, metal oxide nanotubes are monodisperse hollow nanotube, and the length of pipe is 1-5 μm, directly
Diameter is 100-500nm, wall thickness 10-40nm.
Preferably, the modification phase grain diameter is in 2-15nm.
In order to find a kind of method for simply and efficiently preparing the composite air-sensitive material with dispersed nano pipe structure,
It is precursor preparation porous metal oxide method that the application, which is based on existing MOFs, is had effectively achieved in dispersed nano Guan Shangjun
The technical purpose of even dispersion modification phase particle, has prepared the semiconductor gas of the composite construction with high sensitivity and selectivity
Quick material, and improve response and resume speed.For this purpose, a kind of for low concentration of NO the second object of the present invention is to provide2
The In of gas2O3/Sb2O3The preparation method of composite hollow nanotube gas sensitive, comprising:
Matrix material, modification phase raw material and amino terephthalic acid (TPA) (or terephthalic acid (TPA)) are mixed in organic solvent
It is even, solvent structure coordination polymer；
By the centrifugation of above-mentioned coordination polymer, dries and calcine acquisition In2O3/Sb2O3Composite air-sensitive material；
Described matrix raw material includes: InCl3、In(SO4).9H2O、In(NO3)3.4.5H2O、In(NO3)3.xH2One in O
Kind.
The modification phase raw material: SbCl3。
The application research discovery: compared with terephthalic acid (TPA), Sb is more advantageous in MOFs using amino terephthalic acid (TPA)
Doping, thus make building gas sensitive have better response and shorter response recovery time.
Preferably, the modification is mutually the 0.1-10mol% of the mole of basis material.
Preferably, the dosage of the organic coordination polymer amino terephthalic acid (TPA) (or terephthalic acid (TPA)) is basis material
0.1-1.5 times of weight；Preferably 0.2-0.8 times.
There is provided a kind of NO for the third object of the present invention2Gas sensor.
Preferably, the gas sensing layer slurry for containing above-mentioned tandem semiconductor gas sensitive is coated on a ceramic substrate.
It preferably, further include ethyl cellulose and terpinol in the gas sensing layer slurry.
It is furthermore preferred that, using alumina ceramic substrate as carrier, two sides is covered with gold electrode difference using heater-type device architecture
For test electrode and electrode is heated, and has platinum filament extraction electrode, alumina ceramic substrate one side is outer to be coated with gas sensing layer slurry.
Beneficial effects of the present invention
(1) the present invention provides a kind of pair of low concentration of NO2Gas has the novel I n of excellent air-sensitive performance2O3/Sb2O3It is compound
Hollow nanotube gas sensitive.The material surface and pipeline of synthesis are distributed cellular structure, have high specific surface area.Surface and
The modification of inner wall of the pipe distribution mutually air-sensitive response process play adjust gas sensitive resistance variations during the test and
The effect of catalyst is significantly improved to the air-sensitive performance of material.
(2) the Semiconductor gas sensors material of composite construction of the present invention efficiently solves current pure zirconia indium Semiconductor gas sensors material
Existing a series of problem, such as the problem that sensitivity is low, poor selectivity, operating temperature are high and response recovery time is long, and
Expand its application range, reduces production cost.Gas sensor of the invention is directed to the NO of low concentration2Gas have high sensitivity and
Selectivity, can work and response with higher, sensitivity at 50 DEG C -120 DEG C lower temperature.
(3) the Semiconductor gas sensors material scatter of composite construction of the present invention is good, avoid in the preparation process of gas sensor because
Reunite and causes to smear non-uniform problem.
(4) preparation method of the invention and required equipment are simple, easy to operate, and technological parameter is convenient for control, raw material and instrument
Equipment use cost is low etc..
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is unmodified In prepared by comparative example 12O3The electron scanning micrograph of porous nanotube；
Fig. 2 is Sb prepared by embodiment 12O3Modify In2O3The electron scanning micrograph of porous nanotube；
Fig. 3 is Sb prepared by embodiment 12O3Modify In2O3The transmission electron microscope photo of porous nanotube is (high
Times)；
Fig. 4 is Sb prepared by embodiment 12O3Modify In2O3The x-ray photoelectron spectroscopy figure of porous nanotube；
Fig. 5 is Sb prepared by embodiment 12O3Modify In2O3The BET specific surface area spectrogram of porous nanotube and aperture point
Butut；
Fig. 6 is Sb prepared by embodiment 1 and embodiment 22O3Modify In2O3Porous nanotube 3ppm NO2Gas is at 80 DEG C
Under sensitivity response value；
Fig. 7 is In unmodified prepared by comparative example 12O3Sb prepared by porous nanotube and embodiment 12O3Modification
In2O3Porous nanotube is directed to low concentration 3ppm NO2The comparison of air-sensitive performance of the gas at 80 DEG C；
Fig. 8 is Sb prepared by embodiment 12O3Modify In2O3Porous nanotube is directed to NO under various concentration2Gas is at 80 DEG C
Under air-sensitive performance test chart；
Fig. 9 is Sb prepared by embodiment 12O3Modify In2O3Response histogram of the porous nanotube to gas with various；
Figure 10 is Sb prepared by embodiment 12O3Modify In2O3Gas sensor schematic diagram made of porous nanotube: 1, oxygen
Change aluminium ceramic substrate；2, electrode is tested；3 heating electrodes；4, platinum filament；5, gas sensitive figure layer.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive by matrix and is repaired
Phase composition is adornd, described matrix is the metal oxide nanotubes of porous structure, and the metal oxide is selected from In2O3；Described matrix
Modification phase is distributed with inside surface and tube wall；The modification is mutually Sb2O3Nano particle.The tandem semiconductor air-sensitive material
Material is monodisperse hollow nanotube, and the length of pipe is 1-5 μm, diameter 100-500nm, wall thickness 10-40nm.
According to currently preferred, the modification is mutually and the molar ratio of basis material is 0.1-10mol%.
Preferred according to the present invention, the length of the metal oxide nanotubes is 1-5 μm, diameter 100-500nm, wall
Thickness is 10-40nm；The modification phase grain diameter is in 2-15nm.
Preferred according to invention, the specific surface area of the gas sensitive of the composite construction is 90m2g-1-120m2g-1.It is whole
Even size distribution, between average tube diameter about 100-500nm, length is 1-5 μm, wall thickness 10-40nm；In the present invention also referred to as
For modification hollow nanotube.
One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive preparation method, packet
Include that steps are as follows:
(1) by matrix material, modification phase raw material and organic coordination polymer amino terephthalic acid (TPA) (or terephthalic acid (TPA))
It is added in organic solvent dimethylformamide, stirring to dissolution；The clarified solution of acquisition is moved in 50-180 DEG C of oil bath pan and is stirred
5-30min makes raw material that combination reaction occur in oil bath pan, after by product centrifugation, dry and calcine obtain composite construction gas
Quick material；Alternatively,
Organic solvent two is added in matrix material and organic coordination polymer amino terephthalic acid (TPA) (or terephthalic acid (TPA))
In methylformamide, stirring to dissolution；The clarified solution of acquisition is moved in 50-180 DEG C of oil bath pan and stirs 5-30min, makes raw material
Combination reaction occurs in oil bath pan and obtains basis material；By basis material, phase raw material is modified in ultrasonic disperse, addition in ethanol,
Stirring, and ammonium hydroxide is added, it is attached to precipitating inside matrix surface and tube wall；
(2) product for obtaining step (1) is centrifuged, and is cleaned 3-5 times with ethyl alcohol, is dried at 60-80 DEG C；Again as Muffle
400-600 DEG C of calcining 30-90min, obtains the gas sensitive of composite construction in furnace.
Preferred according to the above method, matrix material described in step (1) is selected from InCl3、In(SO4).9H2O、 In
(NO3)3.4.5H2O、In(NO3)3.xH2One of O.
The modification phase raw material is selected from SbCl3。
It is preferred according to the above method, phase raw material is modified in step (1), the molar ratio of matrix material is 0.1-10mol%.
It is preferred according to the above method, organic coordination polymer amino terephthalic acid (TPA) in step (1) (or terephthaldehyde
Acid) dosage be 0.1-1.5 times of basis material weight；It is preferred that 0.2-0.8 times.
The dosage of dimethylformamide is meltage in above-mentioned steps (1).
A kind of NO2The production method of gas sensor, including the above-mentioned novel I n of the present invention2O3/Sb2O3Composite hollow nanotube
The preparation step (1-2) and step (3) of gas sensitive: being made gas sensing layer slurry for the gas sensitive after modification, using spin coating,
Application process makes the coating of gas sensing layer slurry on a ceramic substrate, and NO is made2Gas sensor；
The Semiconductor gas sensors material slurrying of above-mentioned steps (3) composite construction can be by the prior art.Preferably, by composite air-sensitive
Material is added in the solution that ethyl cellulose and terpinol are prepared by 1:8.5-9.5 mass ratio and grinds, and gas sensing layer slurry is made.
The ratio of further preferred composite air-sensitive material and solution quality is 1:3-5.
A kind of more detailed technical solution, a kind of NO2Gas-sensitive sensor device, using heater-type device architecture, with oxidation
Aluminium ceramic substrate is carrier, and it is respectively to test electrode and heating electrode, and have platinum filament extraction electrode that two sides, which is covered with gold electrode, is aoxidized
Aluminium ceramic substrate one side is outer to be coated with gas sensing layer slurry, and the gas sensitive is the above-mentioned composite semiconductor air-sensitive material of the present invention
Material.
The above-mentioned composite semiconductor gas sensitive of the present invention is to low concentration of NO2Gas has highly sensitive and selective, low
Operating temperature is for NO2Application in gas sensitization detection.Operating temperature is 50 DEG C -120 DEG C.
Novel I n of the invention2O3/Sb2O3Composite hollow nanotube gas sensitive, matrix are that size is uniformly hollow
Nanotube, matrix surface and pipeline are distributed a large amount of ducts, and modification is mutually distributed in matrix surface and tube wall inside, particle spherical in shape
Shape.After gas sensor is made, the NO of low concentration2Gas has high sensitivity and selectivity, and optimum working temperature is reduced to
50 DEG C -120 DEG C, response reaches 10-30 times of unmodified basis material, and response and restorability increase.
Present invention will be further explained below with reference to the attached drawings and examples, and implementation is raw materials used to be all made of the commercially available pure examination of analysis
Agent.
Embodiment 1
(1), novel I n2O3/Sb2O3Composite hollow nanotube gas sensitive and preparation
One kind being directed to low concentration of NO2The tandem semiconductor gas sensitive of gas, it is described by matrix and modification phase composition
Matrix is the In of porous structure2O3Modification phase is distributed with inside described matrix surface and tube wall in hollow nanotube；The modification phase
For Sb2O3Nano particle, the modification are mutually 1.5mol% with the molar ratio of basis material.Composite semiconductor gas sensitive is length
Degree is 1-5 μm, diameter 100-500nm, the tubular particle that wall thickness is 10-40nm.
Preparation step:
0.6g matrix material indium nitrate, 7mg are modified into phase raw material antimony chloride, 0.3g organic ligand polymer terephthalic acid (TPA)
Stirring in organic solvent dimethylformamide is added until all dissolutions, the supernatant liquid after stirring, which is placed in oil bath pan, to be stirred
10min makes raw material that combination reaction occur, the product after reaction is centrifugated out, is cleaned with ethyl alcohol, 80 DEG C of drying 6h.It is dry
The final 550 DEG C of calcining 60min in Muffle furnace of good sample, obtain powdered composite semiconductor gas sensitive.
(2), NO is prepared2Gas sensor
Powdered composite air-sensitive material prepared by embodiment 1 is added to ethyl cellulose and terpinol by 1:9 mass ratio
Slurry is made in the solution of configuration, powdered composite air-sensitive material and solution quality ratio are 1:4. as required by above-mentioned air-sensitive material
Slurry material is applied to the one side of ceramic substrate, is prepared into corresponding gas sensitive detection element.Structure is made pottery as described in Figure 10 with aluminium oxide
Ceramic chip 1 is carrier, and it is respectively to test electrode 2 and heating electrode 3, and draw platinum electrode 4, aluminium oxide that two sides face, which is covered with gold electrode,
Gas sensitive 5 is coated with outside 2 faces of ceramic substrate 1.
Sb prepared by embodiment 12O3The porous nanotube In of modification2O3The scanning electron of gas sensitive surface topography is aobvious
It is as shown in Figure 2 that micro mirror analyzes result.From Fig. 2, the material after modification maintains unmodified In2O3The tubular structure of matrix is as schemed
1, advantageous channel is provided for the transport and diffusion of gas, which greatly enhances the specific surface area of gas sensitive and is the suction of gas
It is attached to provide big quantity space with desorption.In addition, modification gas sensitive pattern is uniform and has preferable dispersibility, it is uniformly dispersed.
Fig. 3 is Sb prepared by embodiment 12O3The porous nanotube In of modification2O3The transmission electron microscope high magnification of gas sensitive
Figure.Modify phase Sb2O3In is distributed in spheric granules2O3Matrix surface has responded air-sensitive and has adjusted resistance change in test process
Change and catalyst action.
Fig. 4 is Sb prepared by embodiment 12O3The porous nanotube In of modification2O3The X-ray electron spectrum of gas sensitive
Figure, as seen from the figure, in Sb2O3Modify In2O3In gas sensitive other than the peak of In, O element, there is also the peaks of Sb.Sb2O3Nanometer
The presence of particle is to In2O3The heterojunction structure for playing the role of catalysis and formation of the air-sensitive performance of semiconductor is to In2O3It is surveying
Caused resistance variations play regulating and controlling effect during examination and after gas reaction, substantially increase it to low concentration of NO2Spirit
Sensitivity.Fig. 5 is Sb prepared by embodiment 12O3The porous nanotube In of modification2O3Specific surface area and pore-size distribution map.By
Figure is as it can be seen that the gas sensitive specific surface area with higher modified, value 100.3m2g-1.This is conducive to gas sensitive and mesh
Standard gas body comes into full contact with, and material is made to possess higher sensitivity and response, and gap is evenly distributed, and guarantees material property
Stability.
Fig. 8 is Sb prepared by embodiment 12O3The porous nanotube In of modification2O3Material is directed to NO under different low concentrations2Gas
The air-sensitive performance of body is tested, and as seen from the figure under 80 DEG C of operation temperature, the response of material is with the improve of gas concentration in increasing
High trend, and its response and recovery time shorten with the raising of concentration；There is very high response when concentration reaches 10ppm
Value, response (ratio of the resistance that material is in environment and the resistance in air) are calculated as 235, and response restores
Time is respectively 40s and 40s or so.
Fig. 9 is Sb prepared by embodiment 12O3The porous nanotube In of modification2O3Material is directed to the response of gas with various
Histogram, as seen from the figure, under identical test environment, the material is to NO2The response of gas is much higher than other comparison gases, shows
Brilliant selectivity is shown.
The gas sensitive detection of 2 different modifying phase concentration of embodiment
As described in Example 1, except that modification phase and the molar ratio of basis material are respectively in step (1)
0.5mol%, 1mol%, 2mol%.In 80 DEG C, 3ppm NO2Gas sensitive detection result is as shown in fig. 6, by Fig. 6 under gas condition
It can be seen that having certain variation with the air-sensitive performance of the mole change material of modification phase, but to the NO of 3ppm at 80 DEG C2Gas
Body has relatively good response.Its range responded is 7-30.
Embodiment 3
As described in Example 1, except that: organic ligand polymer be amino terephthalic acid (TPA).Testing result shows:
The material is at 80 DEG C to the low concentration of NO of 3ppm2Response be 128, response recovery time 33s.
Embodiment 4
As described in Example 1, except that: matrix material be 0.6g indium trichloride.Testing result shows: the material in
To the low concentration of NO of 3ppm at 80 DEG C2Response be 104, response recovery time 47s.
Embodiment 5
As described in Example 1, except that: matrix material be 0.3g indium trichloride and 0.3g indium nitrate.Testing result
Show: the material is at 80 DEG C to the low concentration of NO of 3ppm2Response be 128, response recovery time 36s.
The unmodified In of comparative example 12O3Gas sensitive
As described in Example 1, except that: be added without in step (1) modification phase raw material.The unmodified In of gained2O3
Gas sensitive is prepared into corresponding gas sensor as described in Example 1, thus air-sensitive performance testing result is as shown in fig. 7, may be used
The gas sensitive after embodiment 1 is modified is seen in response, response and to be much better than undoped material on recovery time.To 3ppm
Low concentration of NO2Show more excellent performance.Be respectively 116 and 7 with the response of unmodified material after modification, response and
Recovery time foreshortens to 45s and 55s.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (9)
1. one kind is directed to low concentration of NO2The novel I n of gas2O3/Sb2O3The preparation method of composite hollow nanotube gas sensitive,
It is characterized in that, the gas sensitive is made of the modification phase particle of metal oxide nanotubes and modification thereon；
Wherein, metal oxide nanotubes are monodisperse hollow nanotube, and the length of pipe is 1-5 μm, diameter 100-500nm,
Wall thickness is 10-40nm；
Phase grain diameter is modified in 2-15nm；
The preparation method comprises the following steps:
Matrix material, modification phase raw material and amino terephthalic acid (TPA) or terephthalic acid (TPA) are uniformly mixed in organic solvent, it is molten
Agent thermal method synthesizes coordination polymer；
By the centrifugation of above-mentioned coordination polymer, dries and calcine acquisition doped air-sensitive material；
Described matrix raw material includes: InCl3、In(SO4).9H2O、In(NO3)3 .4.5H2O、In(NO3)3 .xH2One of O；
The modification phase raw material: SbCl3。
2. the method as described in claim 1, which is characterized in that the modification is mutually the 0.1- of the mole of matrix material
10mol%.
3. the method as described in claim 1, which is characterized in that the dosage of the amino terephthalic acid (TPA) or terephthalic acid (TPA) is
0.1-1.5 times of matrix material weight.
4. method as claimed in claim 3, which is characterized in that the dosage of the amino terephthalic acid (TPA) or terephthalic acid (TPA) is
0.2-0.8 times of matrix material weight.
5. the low concentration of NO of the described in any item method preparations of claim 1-42The In of gas2O3/Sb2O3Composite hollow nanotube
Gas sensitive.
6. a kind of NO2Gas sensor characterized by comprising composite hollow nanotube gas sensitive described in claim 5.
7. gas sensor as claimed in claim 6, which is characterized in that coating is containing described in claim 5 on a ceramic substrate
Composite hollow nanotube gas sensitive gas sensing layer slurry.
8. gas sensor as claimed in claim 7, which is characterized in that further include ethyl cellulose in the gas sensing layer slurry with
Terpinol.
9. gas sensor as claimed in claim 7 or 8, which is characterized in that heater-type device architecture is used, with aluminium oxide ceramics
Substrate is carrier, and it is respectively to test electrode and heating electrode, and have platinum filament extraction electrode, aluminium oxide ceramics that two sides, which is covered with gold electrode,
Substrate one side is outer to be coated with gas sensing layer slurry.
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| CN110563026A (en) * | 2019-09-03 | 2019-12-13 | 济南大学 | preparation method of rGO composite indium oxide sheet with high gas-sensitive performance |
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