CN108896622A - The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof - Google Patents
The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof Download PDFInfo
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- CN108896622A CN108896622A CN201810436952.6A CN201810436952A CN108896622A CN 108896622 A CN108896622 A CN 108896622A CN 201810436952 A CN201810436952 A CN 201810436952A CN 108896622 A CN108896622 A CN 108896622A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention discloses the SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof, wherein preparation method includes：(1) organic weak base is added into tin tetrachloride ethanol solution, pH to 8-10 is adjusted, and be aged, to obtain tin oxide sol；(2) it disperses ZnO nano-wire in the tin oxide sol, and hexamethylenetetramine is added, to obtain preparatory response liquid；(3) the preparatory response liquid is placed in autoclave and is reacted, and reaction product is filtered, wash and is dried, to obtain the SnO of the heterojunction structure2- ZnO gas sensitive.This method simple process, mild condition, and be easy to be mass produced.The SnO being prepared2- ZnO gas sensitive has multi-level heterojunction structure, can effectively avoid ZnO nano-wire and SnO2The reunion of nano particle, material specific surface area is big, and forms a large amount of hetero-junctions, significantly increases the reactivity site density of material surface, effectively increases response of the sensitive material to multiple gases, assigns gas sensitive excellent gas-sensitive property.
Description
Technical field
The invention belongs to conductor oxidate gas sensor technical fields, specifically, the present invention relates to heterojunction structures
Stannic oxide-zinc oxide gas sensitive and preparation method thereof.
Background technique
Currently, effectively detecting pernicious gas in environment since problem of environmental pollution constantly deteriorates and having great importance.Base
In Metal oxide semiconductor gas-sensitiveness material gas sensor due to sensitivity and gas-selectively adjustable, volume compared with
It is small, cost is relatively low, production it is simple the advantages that, be widely used to industrial production, household safe and environmental sanitation monitoring etc. fields.
Wherein, metal-oxide semiconductor (MOS) gas sensitive material is the core composition of the gas sensor, and performance directly affects gas
The performance and practical application of sensor.Currently, generally being asked existing for the sensor based on Metal oxide semiconductor gas-sensitiveness material
Topic is exactly sensitivity is low, gas-selectively is poor, the response-recovery time is long etc., seriously limits its application field.Therefore, design and
High performance novel semi-conductor gas sensitive is prepared to play a significant role and meaning the performance for improving gas sensor.
Stannic oxide (SnO2) and zinc oxide (ZnO) have always widely as typical two kinds of Semiconductor gas sensors materials
Research and application.In general, the SnO of one-component2Or ZnO has lower sensitivity, poor gas choosing as gas sensitive
Selecting property and longer response time etc..Based on this, at present by SnO2Effectively compound preparation SnO is carried out with ZnO2The compound gas of-ZnO
Quick material causes extensive trial and research.Chinese patent CN106430292A and CN101323975B disclose a kind of hetero-junctions
The ZnO-SnO of structure2Nanocomposite, using CVD method in ZnO or SnO2Nanowire surface grows SnO2Or ZnO nano-wire, shape
At dendroid heterojunction structure, preparation process is cumbersome, and condition is very harsh, and yield is lower, and the serious material that limits is in gas sensing
Promotion and application in device.Chinese patent CN105887465A is prepared for different using the multi-step process such as electrostatic spinning and low temperature water-bath
The ZnO-SnO of matter structure2Composite material, micrometer structure size, complex process are limited to the improvement of air-sensitive performance.Meanwhile China
Patent CN106053556A and Chinese patent CN103776870B is using multistep hydro-thermal method or template in SnO2Nanosphere is received
Popped rice surface modification ZnO nano particle, prepares the ZnO-SnO of heterojunction structure2The ZnO particle of composite material, surface growth is easily rolled into a ball
Poly-, the performance boost for eventually leading to composite air-sensitive material is limited.Chinese patent CN105948105A is using hydro-thermal method in ZnO nano
Stick surface grows SnO2Nanometer rods prepare the ZnO-SnO of heterojunction structure2Composite material, but the covering of ZnO nanorod surface
SnO2Nanometer rods are uneven, are unable to give full play ZnO and SnO2Synergistic effect, air-sensitive performance is promoted will not be significant.Therefore, originally
Invention provides a kind of simple process and prepares a kind of SnO with novel heterojunction structure2- ZnO gas sensitive assigns gas sensor
Outstanding air-sensitive performance.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is stannic oxide-zinc oxide gas sensitive and preparation method thereof of proposition heterojunction structure, and this method passes through in ZnO
Nanowire surface growth in situ modifies SnO2Nano particle significantly increases specific surface area, provides a large amount of reactivity site；
Meanwhile ZnO nano-wire and SnO2A large amount of hetero-junctions can be formed between nano particle, and it is close to further increase reactivity site
Degree.These comprehensive functions will significantly improve response of the gas sensitive to gas, assign gas sensitive excellent gas-sensitive property.
According to an aspect of the present invention, the invention proposes a kind of SnO for preparing heterojunction structure2- ZnO gas sensitive
Method, according to a particular embodiment of the invention, this method includes：
(1) organic weak base is added into tin tetrachloride ethanol solution, pH to 8-10 is adjusted, and be aged, to obtain tin
Colloidal sol；
(2) it disperses ZnO nano-wire in the tin oxide sol, and hexamethylenetetramine is added, to obtain preparatory response
Liquid；
(3) the preparatory response liquid is placed in autoclave and is reacted, and reaction product is filtered, is washed
And drying, to obtain the SnO of the heterojunction structure2- ZnO gas sensitive.
In addition, the SnO according to the above embodiment of the present invention for preparing heterojunction structure2The method of-ZnO gas sensitive can be with
With following additional technical characteristic：
In some embodiments of the invention, the initial concentration of the tin tetrachloride ethanol solution is 0.01-0.1mol/L.
In some embodiments of the invention, the organic weak base is selected from methyl triethylammonium hydroxide, tetrapropyl hydrogen
One of amine-oxides, diethyl-dimethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, trimethylethyl ammonium hydroxide.
In some embodiments of the invention, it is added in the form of aqueous solution of the organic weak base by concentration for 0.05mol/L.
In some embodiments of the invention, in step (1), the ageing is the progress 1-6h completion at 35-70 DEG C.
In some embodiments of the invention, the molar ratio of the ZnO nano-wire and the tin tetrachloride is 1:(0.1-
1)。
In some embodiments of the invention, the molar ratio of the hexamethylenetetramine and the tin tetrachloride is (0.5-
5):1。
In some embodiments of the invention, in step (3), the reaction is the progress 6-20h completion at 160 DEG C.
According to the second aspect of the invention, the invention also provides a kind of SnO of heterojunction structure2- ZnO gas sensitive, root
According to specific embodiments of the present invention, the SnO of the heterojunction structure2- ZnO gas sensitive is by ZnO nano-wire and is formed in the SnO2
The SnO of nanowire surface2Nano particle composition.
In some embodiments of the invention, the diameter of the ZnO nano-wire is 100-300nm, and length is about 2-5 μm,
The SnO2The partial size of nano particle is 20-50nm.
Detailed description of the invention
Fig. 1 is the pure SnO of comparative example preparation2The SEM of nano particle gas sensitive schemes；
Fig. 2 is the SnO with heterojunction structure prepared by embodiment 12The SEM of-ZnO gas sensitive schemes；
Fig. 3 is the SnO with heterojunction structure prepared by embodiment 22The SEM of-ZnO gas sensitive schemes；
Fig. 4 is the SnO with heterojunction structure prepared by embodiment 32The SEM of-ZnO gas sensitive schemes；
Fig. 5 is the SnO with heterojunction structure prepared by embodiment 42The SEM of-ZnO gas sensitive schemes；
Fig. 6 is the SnO with heterojunction structure prepared by embodiment 52The SEM of-ZnO gas sensitive schemes；
Fig. 7 be gas sensor prepared by embodiment 1 and comparative example to the sensitivity of 100ppm alcohol gas with work
Temperature changing curve diagram；
Fig. 8 is spirit of the gas sensor prepared by embodiment 1 and comparative example at 250 DEG C to different concentration ethanol gas
Sensitivity change curve；
Fig. 9 be gas sensor prepared by embodiment 1 and comparative example at 250 DEG C to the sound of 100ppm alcohol gas
Answer-recovery characteristics curve graph；
Figure 10 is embodiment 1 with gas sensor prepared by comparative example at 250 DEG C to 100ppm difference detection gas
Selective figure.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
According to an aspect of the present invention, the invention proposes a kind of SnO for preparing heterojunction structure2- ZnO gas sensitive
Method, according to a particular embodiment of the invention, this method includes：(1) organic weak base is added into tin tetrachloride ethanol solution, adjusts
PH to 8-10, and be aged, to obtain tin oxide sol；(2) it disperses ZnO nano-wire in the tin oxide sol, and is added six
Methine tetramine, to obtain preparatory response liquid；(3) the preparatory response liquid is placed in autoclave and is reacted, and
Reaction product is filtered, wash and is dried, to obtain the SnO of the heterojunction structure2- ZnO gas sensitive.
The SnO for preparing heterojunction structure of the above embodiment of the present invention2By in ZnO nano in the method for-ZnO gas sensitive
Line surface in situ growth modification SnO2Nano particle significantly increases specific surface area, provides a large amount of reactivity site；Together
When, ZnO nano-wire and SnO2A large amount of hetero-junctions can be formed between nano particle, further increase reactivity site density,
Effectively increase response of the sensitive material to multiple gases, assign gas sensitive excellent gas-sensitive property, be conducive to widen its
The application of metal-oxide semiconductor gas sensor domain.
Below to the SnO for preparing heterojunction structure of the above embodiment of the present invention2The method of-ZnO gas sensitive carries out detailed
Description：
According to a particular embodiment of the invention, firstly, organic weak base is added into tin tetrachloride ethanol solution, pH to 8- is adjusted
10, and be aged, to obtain tin oxide sol.
According to a particular embodiment of the invention, the initial concentration of the tin tetrachloride ethanol solution is 0.01-0.1mol/L.
It is possible thereby to which the SnO that uniform particle diameter and size are suitable for is prepared2Nano particle.Pass through the dense of control tin tetrachloride ethanol solution
Degree is conducive to control and generates the rate of precipitation from homogeneous solution and form the particle size of sediment, and finally determines in ZnO nano-wire table
Face generates SnO2Nano particle appearance structure and particle size.
According to a particular embodiment of the invention, organic weak base is added into tin tetrachloride ethanol solution, adjusts pH to 8-10, it is excellent
It is 9 that choosing, which is adjusted to pH,.PH value is adjusted by the way that organic base is added, is conducive to ionization in solution and generates enough hydroxide ions, into
One step reacts completely with tin tetrachloride and generates stannic hydroxide precipitating to form reaction preparation liquid.
Specific example according to the present invention, the organic weak base that above-mentioned adjusting pH is used can be for selected from methyl triethyl group hydrogen-oxygens
Change ammonium, tetrapropylammonium hydroxide, diethyl-dimethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, trimethylethyl hydroxide
One of ammonium.By selecting above-mentioned organic weak base that the SnO being subsequently generated can be effectively prevented2The reunion of nano particle uses
Organic weak base can achieve buffering effect, and pH is slowly increased, and can be conducive to the hydrogen for generating molecule with tin tetrachloride solution
Tin oxide precipitating, and in high pressure hydrothermal reaction process, ammonium ion can promote stannic hydroxide dehydration crystallization to generate target production
The SnO of object nanoscale2Particle, and effectively hinder SnO2The reunion of nano particle.If using inorganic base, such as ammonium hydroxide, then pH
Increase very fast, the stannic hydroxide precipitating of larger particles easily generated.
According to a particular embodiment of the invention, it is added in the form of aqueous solution of the organic weak base by concentration for 0.05mol/L.
From there through the concentration of control organic weak base solution, being slowly increased for system pH can be realized, further generate with tin tetrachloride
The stannic hydroxide of molecule precipitates.Inventors have found that if the excessive concentration of organic weak base solution or too low being unfavorable for obtaining
The sediment of miniature scale.
According to a particular embodiment of the invention, the ageing is the progress 1-6h completion at 35-70 DEG C.From there through ageing
The homogeneity and stability that can be further improved tin oxide sol, by certain time and at a temperature of ageing, can promote precipitating
It recrystallizes, is stablized, the stannic hydroxide of complete crystalline form precipitating inside object.
According to a particular embodiment of the invention, secondly, dispersing ZnO nano-wire in the tin oxide sol that above-mentioned preparation obtains,
And hexamethylenetetramine is added, to obtain preparatory response liquid.In hydrothermal reaction process, hexamethylenetetramine can slowly drop
Solution, system pH slowly rise, and are conducive to SnO2The slow generation and growth of nucleus, and this is also beneficial to SnO2Different growth,
Effectively inhibit SnO2The reunion of nano particle.
According to a particular embodiment of the invention, the additional amount of hexamethylenetetramine can be calculated on the basis of tin tetrachloride.
The molar ratio of specific example according to the present invention, hexamethylenetetramine and tin tetrachloride is (0.5-5):1.Hexa is
On the one hand surfactant and alkali source can promote SnO by controlling the proportion of pregnancy urotropine and tin tetrachloride2Crystallite
It generates, meanwhile, it is capable to as SnO2The surfactant of nanocrystal, effectively obstruction SnO2The reunion of nano particle.Cross major general couple
SnO2The generation and dispersion of nanoparticle play a role it is weaker, excessively also will be to SnO2The aggregation of nano microcrystalline is nucleated and growth produces
Raw inhibiting effect.
According to a particular embodiment of the invention, the molar ratio of ZnO nano-wire and the tin tetrachloride is 1:(0.1-1).By
This is 1 by the molar ratio of control ZnO nano-wire and the tin tetrachloride:(0.1-1) can make finally being capable of ZnO nano-wire
Surface form enough SnO2Nano particle, and then increase specific surface area to the maximum extent.It is received as a result, by controlling ZnO
The proportion of rice noodles and tin tetrachloride, the SnO that effective control ZnO nano-wire surface is finally loaded2The content of nano particle, in turn
Realize suitable SnO2Nano particle is uniformly wrapped on ZnO nano-wire surface, forms a large amount of hetero-junctions to greatest extent, increases
Reactivity site density；And the specific surface area for increasing heterojunction structure provides a large amount of reactivity site, and then significantly changes
The gas-sensitive property of kind gas sensitive.If excessively high, the SnO of ZnO nano-wire surface growth2Serious reunion will occur in nano particle
Behavior seriously reduces specific surface area；If too low, the SnO of ZnO nano-wire area load2Nano particle is limited, is formed a small amount of
Hetero-junctions, reactivity site density are lower.Therefore, it is excessively high it is too low cannot form effective heterojunction structure, can not significantly change
The gas-sensitive property of kind material.
According to a particular embodiment of the invention, it is reacted finally, above-mentioned preparatory response liquid is placed in autoclave,
And reaction product is filtered, wash and is dried, to obtain the SnO of the heterojunction structure2- ZnO gas sensitive.According to this
The specific embodiment of invention, above-mentioned reaction are high temperature hydro-thermal reactions.ZnO nano-wire is dispersed in tin oxide sol and six first first
In urotropine, ZnO nano-wire surface will adsorb SnO2Seed layer.In high temperature hydrothermal reaction process, SnO2Seed layer will be sent out first
Raw dehydrating condensation and crystallization, generate SnO2Nano microcrystalline.Under this high temperature and high pressure environment, the recrystallization of product can be promoted
Effect enhancing, leads to SnO2Crystallite is grown up, and keeps structure more complete.Also, with the extension of reaction time, ZnO nano
The SnO on line surface2Nanocrystal will continue to grow up, and crystallite dimension increases, and by one section of growth phase, pre-reaction material is a large amount of
Consumption, SnO2The partial size of nano particle is up to balance, finally, obtains the SnO of heterojunction structure2-ZnO。
According to a particular embodiment of the invention, above-mentioned reaction is the progress 6-20h completion at 160 DEG C.The reaction is water
Thermal response, high temperature and high pressure environment make Sn (OH)4Dehydrating condensation and crystallization occurs, forms SnO2Nano microcrystalline.Reaction temperature
At 160 DEG C, it can effectively promote Sn (OH)4Dehydrating condensation, improve SnO2Yield.Meanwhile SnO2The recrystallization of product
It is relatively strong, promote SnO2Crystallite grow up and structural integrity.Also, as the reaction time extends, the chance of particle buildup nucleation increases
More, nucleus is constantly grown, and crystal particles size constantly increases, and by controlling the reaction time, can effectively be controlled and is formed by
SnO2The particle size of nano particle.Reaction temperature is excessively high, and grain growth rate is faster, and crystallite dimension increase is faster, formation
SnO2Nanoparticle size is bigger, and is less susceptible to control.Temperature is too low, SnO2Yield reduces, and nucleus growth is slower, crystal knot
Structure is imperfect, influences product property.
According to the second aspect of the invention, the invention also provides a kind of SnO of heterojunction structure2- ZnO gas sensitive, root
According to specific embodiments of the present invention, the SnO of the heterojunction structure2- ZnO gas sensitive is by ZnO nano-wire and is formed in the SnO2
The SnO of nanowire surface2Nano particle composition.
The SnO of the heterojunction structure as a result,2Using ZnO nano-wire as core in-ZnO gas sensitive, SnO2The uniform shape of nano particle
At in SnO2The surface of nano wire, specific structure are referred to the SnO of heterojunction structure in attached drawing 22The SEM of-ZnO gas sensitive schemes
It is shown.Thus the SnO of the heterojunction structure with the structure2- ZnO gas sensitive can significantly increase its specific surface area, important
It is it is possible to prevente effectively from ZnO nano-wire and SnO2The reunion of nano particle, and a large amount of hetero-junctions is formed, significantly increase material
The reactivity site density on surface effectively increases response of the sensitive material to multiple gases, and it is excellent to assign gas sensitive
Gas-sensitive property is conducive to widen it in the application of metal-oxide semiconductor gas sensor domain.
According to a particular embodiment of the invention, the SnO of above-mentioned heterojunction structure2ZnO nano-wire in-ZnO gas sensitive
Diameter is 100-300nm, and length is about 2-5 μm, SnO2The partial size of nano particle is 20-50nm.It is received it is possible thereby to be formed with ZnO
Rice noodles are core, SnO2Nano particle is equably supported on the structure on the surface of ZnO nano-wire.The SnO of the structure2- ZnO air-sensitive material
Material can significantly increase its specific surface area, and then provide a large amount of reactivity site；Meanwhile it being formed at two-phase interface a large amount of
Hetero-junctions, and then reactivity site density can be dramatically increased, further promote the performance of gas sensitive.Compared to pure ZnO
Nano wire and SnO2Nano particle, the SnO with heterojunction structure2- ZnO gas sensitive can integrate ZnO and SnO2Excellent spy
Property, and realize efficient chemiluminescence, be conducive to widen it in the application of gas sensor domain.
Compared with prior art, the SnO for preparing heterojunction structure of the above embodiment of the present invention2The method of-ZnO gas sensitive
And the SnO for the heterojunction structure being prepared2- ZnO gas sensitive at least has one of following advantages：
1, the SnO of heterojunction structure prepared by the present invention2- ZnO gas sensitive, preparation process is simple, mild condition, is easy to big
Large-scale production.
2, SnO prepared by the present invention2- ZnO gas sensitive has heterojunction structure, significantly increases specific surface area, provides big
The reactivity site of amount；Meanwhile a large amount of hetero-junctions is formed at two-phase interface, reactivity site density is dramatically increased, into
The performance of one step promotion gas sensitive.Compared to pure ZnO nano-wire and SnO2Nano particle, the SnO with heterojunction structure2-ZnO
Gas sensitive can integrate ZnO and SnO2Excellent characteristics, and realize efficient chemiluminescence, be conducive to widen it in gas
The application in body sensor field.
3, the SnO of the heterojunction structure prepared by the present invention2- ZnO gas sensitive is by ZnO nano-wire and SnO2Nano particle
Assemble.The appearance structure of gas sensitive can effectively be regulated and controled by modulation process parameter and reaction condition, assign material
Adjustable gas-sensitive property, to meet the performance requirement of different field.
Comparative example
(1) pure SnO is prepared2Nano particle：
0.15mol/L tin tetrachloride aqueous solution is prepared first；The ammonia spirit of 5mol/L is added dropwise to tin tetrachloride
In aqueous solution, mixed solution is transferred in hydrothermal reaction kettle, 160 DEG C of reaction 12h.Product is filtered, washed, dry to get
Pure SnO2Nano particle.
(2) analysis test：
To the pure SnO being prepared2Nano particle is observed under scanning electron microscope, the result is shown in Figure 1.
Gas sensor element, and the test performance on WS-30A air-sensitive tester is made in prepared sensitive material.
Specifically conventional method includes：
A：By with a pair of of gold electrode and four Pt leads ceramic tube and Ni-Cr alloy heater strip be welded on six
On leg base；
B：The gas sensitive material of 600 DEG C of 2h that anneal is added to volume ratio 1:In the 2 water-ethanol mixed solutions being made into,
It grinds 30min and it is coated on to ceramic pipe surface to certain density slurry, and the dry 12h at 90 DEG C, obtain gas biography
Sensor component.
C：The sensor element of aging 5 days is subjected to gas-sensitive property test using WS-30A air-sensitive tester.Measure voltage
5V, heating voltage are adjustable.
(3) conclusion：
1, it is shown by Fig. 1, pure SnO2Nano particle diameter about 50nm, but there is serious reunion behavior.
2, gas sensor, and the test performance on WS-30A air-sensitive tester is made in prepared sensitive material.Wherein,
Sensitivity S=Ra/Rg of gas sensor, Rg be gas sensor test gas in resistance value, Ra be gas sensor in air
Resistance value.Test result such as Fig. 7, shown in 8,9,10.The optimum working temperature of gas sensor is 250 DEG C.At 250 DEG C, air-sensitive
Element is respectively 3.8,5.5,7.4,9.8,14.4 to the sensitivity S of 10,20,30,40,60,80,100ppm alcohol gas,
18.7 21.2.Meanwhile gas sensor is respectively 18.65 to the sensitivity S of the methanol of 100ppm, acetone, formaldehyde and toluene,
11.55,6.54,3.64.Response time and recovery time are 16s and 24s respectively.
Embodiment 1
(1) SnO of heterojunction structure2- ZnO gas sensitive：
Prepare tin oxide sol：The methyl triethylammonium hydroxide aqueous solution of 0.05mol/L is added to the four of 0.02mol/L dropwise
In stannic chloride ethanol solution, until system pH~9；And 3h is aged at 50 DEG C and obtains tin oxide sol.By 0.81g ZnO nano-wire point
It dissipates in above-mentioned tin oxide sol, and 0.14g hexamethylenetetramine is added, then mixed solution is transferred in hydrothermal reaction kettle, in
10h is reacted at 160 DEG C, is filtered, washed the dry SnO to get heterojunction structure2- ZnO gas sensitive.
(2) analysis test：
SnO to the heterojunction structure being prepared2- ZnO gas sensitive is observed under scanning electron microscope, as a result sees Fig. 2.
Gas sensor element, and the testability on WS-30A gas sensor tester is made in prepared sensitive material
Can, the same comparative example of test method.
(3) conclusion：
As shown in Figure 2, the SnO for the heterojunction structure being prepared2The SnO of-ZnO surface modification2Nano particle diameter is about
30nm。
Air-sensitive performance test result such as Fig. 7, shown in 8,9,10, the best effort temperature of gas sensor prepared by the present embodiment
Degree is 250 DEG C.At 250 DEG C, gas sensor is respectively to the sensitivity S of 10,20,30,40,60,80,100ppm alcohol gas
11.41,18.5,23.47,31.12,43.85,54.42,59.64.Meanwhile gas sensor is to the methanol, acetone, first of 100ppm
The sensitivity S of aldehyde and toluene is respectively 32.82,27.53,17.5,9.46.Response time and recovery time are 8s and 19s respectively.
It can be seen that based on the SnO of heterojunction structure prepared by the present embodiment2The sensitivity of the gas sensor of-ZnO gas sensitive is obvious
Higher than gas sensor prepared by comparative example, and there is more quickly response and recovery.
Embodiment 2
(1) the methyl triethylammonium hydroxide aqueous solution of 0.05mol/L is added to the tin tetrachloride second of 0.03mol/L dropwise
In alcoholic solution, until system pH~9；And 3h is aged at 50 DEG C and obtains tin oxide sol.It disperses 0.61g ZnO nano-wire in above-mentioned
In tin oxide sol, and 0.42g hexamethylenetetramine is added, then mixed solution is transferred in hydrothermal reaction kettle, it is anti-at 160 DEG C
10h is answered, the dry SnO to get heterojunction structure is filtered, washed2- ZnO gas sensitive.
(2) analysis test：
SnO to the heterojunction structure being prepared2- ZnO gas sensitive is observed under scanning electron microscope, as a result sees Fig. 3.
(3) conclusion：
It is shown by Fig. 3, the SnO for the heterojunction structure being prepared2The SnO of-ZnO surface modification2Nano particle diameter is about
20nm。
Embodiment 3
(1) tin oxide sol is prepared：The methyl triethylammonium hydroxide aqueous solution of 0.05mol/L is added into 0.04mol/L dropwise
Tin tetrachloride ethanol solution in, until system pH~9；And 3h is aged at 50 DEG C and obtains tin oxide sol.(2) heterojunction structure is prepared
SnO2- ZnO gas sensitive：It disperses 0.54g ZnO nano-wire in above-mentioned tin oxide sol, and six methine four of 0.84g is added
Mixed solution is then transferred in hydrothermal reaction kettle by amine, reacts 10h at 160 DEG C, is filtered, washed dry to get hetero-junctions
The SnO of structure2- ZnO gas sensitive.
(2) analysis test：
SnO to the heterojunction structure being prepared2- ZnO gas sensitive is observed under scanning electron microscope, as a result sees Fig. 4.
(3) conclusion：
It is shown by Fig. 4, the SnO for the heterojunction structure being prepared2The SnO of-ZnO surface modification2Nano particle diameter is about
20nm。
Embodiment 4
(1) tin oxide sol is prepared：The methyl triethylammonium hydroxide aqueous solution of 0.05mol/L is added into 0.05mol/L dropwise
Tin tetrachloride ethanol solution in, until system pH~9；And 3h is aged at 50 DEG C and obtains tin oxide sol.(2) heterojunction structure is prepared
SnO2- ZnO gas sensitive：It disperses 0.51g ZnO nano-wire in above-mentioned tin oxide sol, and six methine four of 1.4g is added
Mixed solution is then transferred in hydrothermal reaction kettle by amine, reacts 10h at 160 DEG C, is filtered, washed dry to get hetero-junctions
The SnO of structure2- ZnO gas sensitive.
(2) analysis test：
SnO to the heterojunction structure being prepared2- ZnO gas sensitive is observed under scanning electron microscope, as a result sees Fig. 5.
(3) conclusion：
It is shown by Fig. 5, the SnO for the heterojunction structure being prepared2The SnO of-ZnO surface modification2Nano particle diameter is about
20nm。
Embodiment 5
(1) tin oxide sol is prepared：The methyl triethylammonium hydroxide aqueous solution of 0.05mol/L is added into 0.06mol/L dropwise
Tin tetrachloride ethanol solution in, until system pH~9；And 3h is aged at 50 DEG C and obtains tin oxide sol.(2) heterojunction structure is prepared
SnO2- ZnO gas sensitive：It disperses 0.49g ZnO nano-wire in above-mentioned tin oxide sol, and six methine four of 2.1g is added
Mixed solution is then transferred in hydrothermal reaction kettle by amine, reacts 10h at 160 DEG C, is filtered, washed dry to get hetero-junctions
The SnO of structure2- ZnO gas sensitive.
(2) analysis test：
SnO to the heterojunction structure being prepared2- ZnO gas sensitive is observed under scanning electron microscope, as a result sees Fig. 6.
(3) conclusion：
It is shown by Fig. 6, the SnO for the heterojunction structure being prepared2The SnO of-ZnO surface modification2Nano particle diameter is about
10nm, and there is a degree of agglomeration.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of SnO for preparing heterojunction structure2The method of-ZnO gas sensitive, which is characterized in that including：
(1) organic weak base is added into tin tetrachloride ethanol solution, pH to 8-10 is adjusted, and be aged, to obtain tin oxide sol；
(2) it disperses ZnO nano-wire in the tin oxide sol, and hexamethylenetetramine is added, to obtain preparatory response liquid；
(3) the preparatory response liquid is placed in autoclave and is reacted, and reaction product is filtered, wash and is done
It is dry, to obtain the SnO of the heterojunction structure2- ZnO gas sensitive.
2. the method according to claim 1, wherein the initial concentration of the tin tetrachloride ethanol solution is
0.01-0.1mol/L。
3. the method according to claim 1, wherein the organic weak base is selected from methyl triethyl group hydroxide
Ammonium, tetrapropylammonium hydroxide, diethyl-dimethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, trimethylethyl ammonium hydroxide
One of.
4. according to the method described in claim 3, it is characterized in that, the organic weak base with concentration is the water-soluble of 0.05mol/L
Liquid form is added.
5. method according to claim 1-4, which is characterized in that in step (1), the ageing is in 35-70
1-6h completion is carried out at DEG C.
6. method according to claim 1-4, which is characterized in that the ZnO nano-wire and the tin tetrachloride
Molar ratio be 1:(0.1-1).
7. according to the method described in claim 6, it is characterized in that, mole of the hexamethylenetetramine and the tin tetrachloride
Than for (0.5-5):1.
8. method according to claim 1 or claim 7, which is characterized in that in step (3), the reaction is carried out at 160 DEG C
What 6-20h was completed.
9. a kind of SnO of heterojunction structure2- ZnO gas sensitive, which is characterized in that the SnO of the heterojunction structure2- ZnO gas sensitive
By ZnO nano-wire and it is formed in the SnO2The SnO of nanowire surface2Nano particle composition.
10. the SnO of heterojunction structure according to claim 92- ZnO gas sensitive, which is characterized in that the ZnO nano-wire
Diameter be 100-300nm, length is about 2-5 μm, the SnO2The partial size of nano particle is 20-50nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110068597A (en) * | 2019-05-05 | 2019-07-30 | 吉林大学 | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof |
| CN110161087A (en) * | 2019-05-20 | 2019-08-23 | 南京工业大学 | A kind of preparation and application of hydrogen sensing material |
| JP2019178887A (en) * | 2018-03-30 | 2019-10-17 | 日本特殊陶業株式会社 | Gas sensor |
| CN110589875A (en) * | 2019-09-17 | 2019-12-20 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| CN111272825A (en) * | 2020-03-06 | 2020-06-12 | 电子科技大学中山学院 | Metal oxide gas sensor based on surface plasmon enhancement |
| CN111349974A (en) * | 2020-03-12 | 2020-06-30 | 重庆大学 | Preparation method of nanofiber hydrogen sensing material subjected to plasma treatment |
| CN111579600A (en) * | 2020-06-28 | 2020-08-25 | 郑州轻工业大学 | Camellia flower-shaped ZnO/SnO-SnO2Composite material and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549995A (en) * | 2009-05-12 | 2009-10-07 | 西北大学 | ZnO@SnO2 cladding material and preparing method thereof |
| CN103274451A (en) * | 2013-05-14 | 2013-09-04 | 东华大学 | Synthesis and application of nanometer composite material with stannic oxide/zinc oxide core-shell structure |
| KR20140139641A (en) * | 2013-05-24 | 2014-12-08 | 인하대학교 산학협력단 | ZnO-SnO2 nanofiber-nanowire stem-branch heterostructure material and preparation method thereof and gas sensor containing the material |
| US20160041116A1 (en) * | 2014-08-06 | 2016-02-11 | Korea Advanced Institute Of Science And Technology | Composite metal oxide materials including polycrystalline nanofibers, microparticles, and nanoparticles, gas sensors using the same as a sensing material thereof, and manufacturing methods thereof |
| CN105887465A (en) * | 2016-05-30 | 2016-08-24 | 大连民族大学 | Same type (n-n) heterogeneous structure SnO2/ZnO nano-composite fiber material and preparation method and application thereof |
| 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 |
-
2018
- 2018-05-09 CN CN201810436952.6A patent/CN108896622B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549995A (en) * | 2009-05-12 | 2009-10-07 | 西北大学 | ZnO@SnO2 cladding material and preparing method thereof |
| CN103274451A (en) * | 2013-05-14 | 2013-09-04 | 东华大学 | Synthesis and application of nanometer composite material with stannic oxide/zinc oxide core-shell structure |
| KR20140139641A (en) * | 2013-05-24 | 2014-12-08 | 인하대학교 산학협력단 | ZnO-SnO2 nanofiber-nanowire stem-branch heterostructure material and preparation method thereof and gas sensor containing the material |
| US20160041116A1 (en) * | 2014-08-06 | 2016-02-11 | Korea Advanced Institute Of Science And Technology | Composite metal oxide materials including polycrystalline nanofibers, microparticles, and nanoparticles, gas sensors using the same as a sensing material thereof, and manufacturing methods thereof |
| 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 |
| CN105887465A (en) * | 2016-05-30 | 2016-08-24 | 大连民族大学 | Same type (n-n) heterogeneous structure SnO2/ZnO nano-composite fiber material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIWEI WANG,ET AL.: "Construction of 1D SnO2-coated ZnO nanowire heterojunction for their improved n-butylamine sensing performances", 《SCIENTIFIC REPORTS》 * |
| 赵天 等: "ZnO/SnO2核壳结构染料敏化太阳能电池性能研究", 《合肥工业大学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019178887A (en) * | 2018-03-30 | 2019-10-17 | 日本特殊陶業株式会社 | Gas sensor |
| JP6994717B2 (en) | 2018-03-30 | 2022-01-14 | 日本特殊陶業株式会社 | Gas sensor and gas sensor manufacturing method |
| CN110068597A (en) * | 2019-05-05 | 2019-07-30 | 吉林大学 | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof |
| CN110161087A (en) * | 2019-05-20 | 2019-08-23 | 南京工业大学 | A kind of preparation and application of hydrogen sensing material |
| CN110589875A (en) * | 2019-09-17 | 2019-12-20 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| CN110589875B (en) * | 2019-09-17 | 2021-10-26 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| CN111272825A (en) * | 2020-03-06 | 2020-06-12 | 电子科技大学中山学院 | Metal oxide gas sensor based on surface plasmon enhancement |
| CN111349974A (en) * | 2020-03-12 | 2020-06-30 | 重庆大学 | Preparation method of nanofiber hydrogen sensing material subjected to plasma treatment |
| CN111579600A (en) * | 2020-06-28 | 2020-08-25 | 郑州轻工业大学 | Camellia flower-shaped ZnO/SnO-SnO2Composite material and preparation method and application thereof |
| CN111579600B (en) * | 2020-06-28 | 2022-11-22 | 郑州轻工业大学 | Camellia flower-shaped ZnO/SnO-SnO 2 Composite material and preparation method and application thereof |
| CN112058253A (en) * | 2020-09-29 | 2020-12-11 | 西安建筑科技大学 | Three-dimensional structure core-shell nano ZnO @ In2O3Preparation method of photocatalytic material |
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