CN106770501A - A kind of alcohol gas sensor based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and preparation method thereof - Google Patents
A kind of alcohol gas sensor based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and preparation method thereof Download PDFInfo
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Abstract
A kind of alcohol gas sensor based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and preparation method thereof, belongs to oxide semiconductor gas sensor technical field.The present invention is first using Zinc diacetate dihydrate, glycine, Disodium sulfate decahydrate, NaOH as the raw material that sets out, the mixed solution of water and ethanol is used as solvent, the hollow bouquet presomas of ZnO are successfully prepared using hydro-thermal method, then calcining has obtained the hollow bouquet powder of ZnO in atmosphere；Again using the hollow bouquet powder of ZnO, four nitric hydrate cadmiums, thiocarbamide as the raw material that sets out, the mixed solution of dimethylformamide (DMF) and isopropanol is used as solvent, CdO nano particles are combined on the hollow bouquets of ZnO using hydro-thermal method, then calcining obtains the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials in atmosphere.Instant invention overcomes the shortcoming that two kinds of material gas-sensitive properties are poor, the raising and the reduction of Monitoring lower-cut to alcohol gas detection sensitivity are realized.
Description
Technical field
The invention belongs to oxide semiconductor gas sensor technical field, and in particular to one kind is based on the hollow bouquets of ZnO
With the alcohol gas sensor of CdO nano-particles reinforcement nano materials and preparation method thereof.
Background technology
We are in the information age that artificial intelligence and Internet of Things emerge, in the chain of the acquisition-transmission-treatment to information
In bar, sensor is sent out as the front-end devices of the information of the acquisition sensorium complicated equivalent to the mankind in information technology chain
Wave vital effect.Gas sensor as member important in sensor family, in fields such as safety, environment, medical treatment
Play very important effect.Gas sensor species is various, and sorting technique is also varied.Based oxide semiconductor
Gas sensor has that sensitivity is high, adjustable, reliability is high, all solid state for selectivity, the low outstanding advantages of cost, is current gas
The main flow of sensory field research, its commercial quantities are also maximum.Although we are in the research of oxide semiconductor gas sensor
Very big progress is had been obtained for, but in order to further expand its application field, in addition it is also necessary to further improve gas sensor
Gas-sensitive property.
So far, the research on oxide semiconductor be around how to improve its sensitivity, selectivity, detection essence
Degree and reliability and launch, specifically include the discovery of new gas sensitive material, sensitive material modified (doping, surface are repaiied
Decorations, Material cladding etc.) and sensor mechanism further investigation etc..Wherein, Kyushu University N.Yamazoe seminar is in 21 century
Just carry out to compare in terms of the selectivity of gas sensitive, transformation efficiency and utilization rate three and goed deep into systematic research.Based on
Upper three aspects, it has been found that can significantly improve sensor by constructing heterojunction structure semiconductor oxide composite
Sensitivity.This is primarily due to the carrier mobility that heterojunction structure improves sensing material, so as to improve its " conversion
Function ", secondly, under nanoscale, the compound and assembling of different oxide semiconductor sensing materials can form local P-N
Cooperative effect between contact, N-N contacts and different component, improves " identification function " of sensing material.Based on this point, carry out
The design and preparation of heterojunction structure oxide semiconductor, for the application of enlargement gas sensor there is highly important science to anticipate
Justice.
Heterojunction structure nanosensor material character is steady, affected by environment small, improves the stability of sensor.ZnO
As a kind of common N-type oxide semiconductor gas sensitive, the inspection of various toxic and harmfuls is widely used at present
Survey, but because its poor, operating temperature of selectivity is higher, therefore, also need by between ZnO and other oxide semiconductors
Heterojunction structure is built, further to improve the gas sensing characteristic of pure ZnO nano-structure.CdO is used as a kind of important
II-VI races low energy gap N-type semiconductor oxide, because there is natural defect Lacking oxygen in its lattice, has high load
Stream transport factor and high conductivity.Therefore based on the hollow bouquets of ZnO and CdO nano-particles reinforcements nano material in sensitivity, choosing
The many aspects such as selecting property, operating temperature, response resume speed are better than the hollow bouquets of ZnO.Significantly improving for gas-sensitive property can
It is attributed to following aspects：The increase of chemically adsorbing oxygen quantity, N-N heterojunction structures are constructed and treasure maesa herb spherical structure profit
In gas molecule diffusion.This is to a certain extent, it was demonstrated that composite oxide semiconductor be expected to turn into it is a kind of it is new very
Gas sensitive with application prospect
The content of the invention
It is contemplated that being changed by constructing the nanostructured based on the hollow bouquets of ZnO and CdO nano-particles reinforcements multiple
Condensation material pattern, improve carrier concentration and form potential barrier etc., it is real so as to come the shortcoming that overcomes two kinds of material gas-sensitive properties poor
Sensitivity raising and the reduction of Monitoring lower-cut now to alcohol gas detection.
The present invention is first using Zinc diacetate dihydrate, glycine, Disodium sulfate decahydrate, NaOH as the raw material that sets out, water
With the mixed solution of ethanol as solvent, the hollow bouquet presomas of ZnO are successfully prepared using hydro-thermal method, then forged in atmosphere
Burning has obtained the hollow bouquet powder of ZnO；Again using the hollow bouquet powder of ZnO, four nitric hydrate cadmiums, thiocarbamide as the raw material that sets out, two
The mixed solution of NMF (DMF) and isopropanol is combined CdO and receives as solvent, using hydro-thermal method on the hollow bouquets of ZnO
Rice grain, then calcining obtains the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials in atmosphere.
Of the present invention is a kind of alcohol gas based on the hollow bouquets of ZnO Yu CdO nano-particles reinforcement nano materials
Sensor, device is heater-type gas sensor, carries two ring-types by outer surface, is parallel to each other and gold electrode separate
Alumina ceramic tube, nichrome heating coil, sensitive material coating composition；Nichrome heating coil is passed through in earthenware
Portion, for the normal work of sensor provides suitable temperature, it is characterised in that：Sensitive material is the hollow bouquets of ZnO and CdO nanometers
Particles dispersed nano material, and prepared by following steps,
(1) first by the Zn (CH of 0.4~0.8g3COO)2·2H2O, the glycine of 0.4~0.8g, 0.4~0.8g
Na2SO4·10H2O is added sequentially in the mixed solvent of 10~15mL deionized waters and 10~15mL ethanol, and stirring 10~
The NaOH of 0.4~0.8g is added after 20min, then stirring is until well mixed；
(2) above-mentioned solution is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, then stainless steel cauldron exists
10~14h of hydro-thermal reaction at 160~180 DEG C, after being cooled to room temperature, the precipitation deionized water and ethanol that will be collected into alternately from
The heart is cleaned 5~7 times, is then dried at 70~90 DEG C, calcines 1~2h at 400~500 DEG C again afterwards, obtains ZnO treasure maesa herbs
Ball powder, its a diameter of 2~3 μm, the hollow bouquet hetero-junctions of ZnO is formed by nanometer sheet is interspersed, its part nanometer sheet
Thickness is 60~70nm；
(3) again by the hollow bouquet powder of the ZnO of 0.03~0.05g, the Cd (NO of 0.003~0.024g3)2·4H2O and
The CH of 0.0108~0.0216g4N2S is added sequentially in the DMF of the isopropanol containing 200~400 μ L and 25~30mL, stirring
20~30min of ultrasound after 10~20min is until form homogeneous mixture solotion；
(4) solution obtained in step (3) is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, then by stainless steel
Reactor 8~12h of hydro-thermal reaction at 150~170 DEG C, after being cooled to room temperature, the precipitation deionized water and second that will be collected into
Alcohol alternating centrifugal is cleaned 5~7 times, is then dried at 70~90 DEG C, calcines 1~2h at 450~550 DEG C again afterwards, is obtained
The hollow bouquets of ZnO and CdO nano-particles reinforcement nano material powder；A diameter of 9~12nm of CdO nano particles.
Wherein, the length of earthenware is 4~4.5mm, and external diameter is 1.2~1.4mm, and internal diameter is 0.8~0.9mm, 2 annulars
The width of gold electrode is 0.8~0.9mm, and two electrode spacings are 1.8~2.0mm, and two platinum filaments are connected with each gold electrode
Make pin, the length of platinum filament is 9~10mm, and resistance is 38~40 Ω.
The invention provides a kind of alcohol gas based on the hollow bouquets of ZnO Yu the nano material of CdO nano-particles reinforcements
Transducer production method, its step is as follows：
(1) by the hollow bouquets of ZnO and CdO nano-particles reinforcement nano material powder and deionized water in mass ratio 3~5：1
Mixing, and grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two with brush
Ring-type, be parallel to each other and gold electrode separate aluminium oxide ceramics pipe surface, formed 20~30 μ m-thicks sensitive material apply
Layer, and make sensitive material that annular gold electrode is completely covered；
(2) alumina ceramic tube that will scribble sensitive material toasts 20~30min at being 80 DEG C~100 DEG C in temperature, treats
After sensitive material is dried, alumina ceramic tube is calcined 2~5h at 400~500 DEG C；Then it is 20~30 by a resistance value
Ω, the number of turn are that the nichrome heating coil of 30~40 circles is passed as heater strip, finally by above-mentioned device from ceramic tube inside
Welded and encapsulated according to heater-type gas sensor, just obtained based on the hollow bouquets of ZnO and CdO nano-particles reinforcements nanometer
The heater-type alcohol gas sensor of material.
Heater-type alcohol gas sensor of the present invention is using the hollow bouquets of ZnO and CdO nano-particles reinforcements nanometer
Material is used as sensitive material.Its mechanism is：First, heterojunction structure treasure maesa herb ball has hollow structure and specific surface area is big, institute
To increase the response area of target gas molecules and oxygen molecule, greatly increase the utilization rate of element material；On the other hand,
Unique heterojunction structure can also help improve the gas sensitization characteristic of device.By theory analysis it may be concluded that sensitivity
The resistance of material is strongly depend on the potential barrier of its crystal inside interface.Material synthesized by us, the hollow bouquets of ZnO and CdO
Contact between nano particle forms N-N hetero-junctions, increased barrier height, and material resistance is changed greatly in making course of reaction,
So as to contribute to the raising of gas-sensitive property；The collective effect of these two aspects greatly improved the sensitivity of sensor.Meanwhile, this hair
The bright hollow bouquets of used ZnO are environmentally friendly with the synthetic method of CdO nano-particles reinforcement nano materials, with low cost；Make
Heater-type sensor process is simple, small volume, beneficial to industrial batch production, therefore is detected in medical treatment, industry security control etc.
Aspect has broad application prospects.
Brief description of the drawings
Fig. 1 is that the hollow bouquets of ZnO of the invention are schemed with the SEM of CdO nano-particles reinforcement nano materials, wherein (a) figure
Multiplication factor is 6000 times, and the multiplication factor of (b) figure is 20000 times, and the multiplication factor of (c) figure is 200000 times；
Fig. 2 is that the alcohol gas based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials prepared by the present invention are passed
The structural representation of sensor；
Fig. 3 be comparative example of the invention and embodiment 1, embodiment 2, embodiment 3 and in embodiment 4 sensor in different works
To the Sensitivity comparison figure of 100ppm ethanol at a temperature of work；
Fig. 4 be comparative example of the invention and embodiment 1, embodiment 2, embodiment 3 and in embodiment 4 sensor in work temperature
Spend for 250 DEG C when to the selective column diagram of 100ppm gas with various；
Fig. 5 be comparative example of the invention and embodiment 1, embodiment 2, embodiment 3 and in embodiment 4 sensor in work temperature
Spend for 250 DEG C when device sensitivity-concentration of alcohol characteristic curve.
As shown in figure 1, it can be seen that the hollow bouquets of ZnO are treasure maesa herb with CdO nano-particles reinforcements nano material in (a) figure
Spherical structure, good dispersion, a diameter of 2~3 μm of the hollow bouquets of ZnO；The hollow bouquets of ZnO and CdO nano particles are found out in (b) figure
Composite nano materials are assembled by ZnO nano piece, and ZnO nano piece outwards dissipates；It can be seen that CdO nanometers in (c) figure
Even particulate dispersion on ZnO nano piece, a diameter of 9~12nm of CdO nano particles.
As shown in Fig. 2 the alcohol gas sensor based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials by
Alumina ceramic tube 1, semiconductor sensitive material 2, nickel-cadmium heating coil 3, annular gold electrode 4 and platinum filament pin 5 are constituted.
As shown in figure 3, comparative example and embodiment 1, embodiment 2, embodiment 3 and in embodiment 4 sensor best effort
Temperature is 250 DEG C, and now sensitivity of the device to 100ppm ethanol is respectively 7.7,12.3,35.2,65.5 and 15.6.
As shown in figure 4, comparative example and embodiment 1, embodiment 2, embodiment 3 and sensor has to ethanol in embodiment 4
There is highest sensitivity.And compared in comparative example, the selectivity of sensor is greatly improved in all embodiments.
As shown in figure 5, when device operating temperature is 250 DEG C, the sensitivity of all devices is with the increasing of concentration of alcohol
Plus and increase, and growth trend gradually slows down.Wherein, sensor sheet reveals optimal gas-sensitive property in embodiment 3.When ethanol is dense
When degree increases to 100ppm, it still maintains good linear relationship, and sensor has test wider in showing embodiment 3
Scope.
The electric current of heating coil is flowed through by changing to regulate and control the operating temperature of sensor, is in not by measurement sensor
Resistance value during with gas between two gold electrodes can obtain the sensitivity of sensor.Spirit of the sensor for alcohol gas
Sensitivity S is defined as：S=Ra/Rg, wherein RaAnd RgRespectively electricity of sensor when in air and alcohol gas between two gold electrodes
Resistance.By sensitivity and gas concentration characteristic curve, it is possible to achieve the measurement to unknown ethanol gas concentration.
Specific embodiment
Comparative example：
Heater-type alcohol gas sensor is made as sensitive material using the hollow bouquets of ZnO, its specific manufacturing process is such as
Under：
1. first by the Zn (CH of 0.439g3COO)2·2H2O (Zinc diacetate dihydrate) be added to 10mL deionized waters and
In the mixed solution of 15mL ethanol, it is kept stirring for until it is all after dissolving, then by 0.4g glycine, 0.4g Na2SO4·
10H2O (Disodium sulfate decahydrate) is added in above-mentioned solution, and 0.4g NaOH (NaOH) is added after stirring 5min, continues to stir
1h；
2. by above-mentioned solution at 180 DEG C hydro-thermal reaction 12h, after being cooled to room temperature, by the precipitation deionized water of generation
With ethanol alternating centrifugal clean 7 times, then at 80 DEG C dry, calcine 2h at 400 DEG C again afterwards, finally just obtained by
The hollow bouquet powder of ZnO that ZnO nano piece assembles；
3. by the hollow bouquet powder of sensitive material ZnO and deionized water in mass ratio 5:1 mixing, and grinding forms pasty state slurry
Material, then with brush by above-mentioned slurry be uniformly coated on commercially available outer surface with two ring-types, be parallel to each other and divide each other
The aluminium oxide ceramics pipe surface of vertical gold electrode, forms the sensitive material film of 30 μ m-thicks, and makes sensitive material that ring is completely covered
Shape gold electrode；Wherein, the length of earthenware is 4mm, and external diameter is 1.2mm, and internal diameter is 0.8mm, and the width of 2 annular gold electrodes is
0.8mm, two electrode spacings are 1.8mm, two platinum filaments are connected with each gold electrode and make pin, and the length of platinum filament is 9mm；
4. the alumina ceramic tube that sensitive material will be scribbled toasts 30min at 90 DEG C, after after sensitive material drying, oxygen
Change during aluminium earthenware is put into Muffle furnace and calcine 2h at 400 DEG C；Then a resistance value is 30 Ω, the nickel chromium triangle that the number of turn is 40 circles
Alloy heating coil is passed as heater strip from ceramic tube inside, and finally above-mentioned device is welded according to heater-type gas sensor
Connect and encapsulate, just obtained the heater-type alcohol gas sensor based on the hollow bouquets of ZnO.
Embodiment 1：
With Cd:Zn mol ratios 0.44:100 (this ratio is within the raw material dosage scope described in the content of the inventionIt is
) the hollow bouquets of ZnO of preparation make alcohol gas sensor with CdO nano-particles reinforcements nano material as sensitive material,
Its specific manufacturing process is as follows：
1. first by the hollow bouquet powder of 30mg ZnO, the Cd (NO of 0.003g3)2·4H2O (four nitric hydrate cadmiums),
The CH of 0.006g4N2S (thiocarbamide) is added sequentially to 30mL DMF, is kept stirring for until it is all after dissolving, then by 300 μ L isopropyls
Alcohol is added in above-mentioned solution, continues to stir 10min, ultrasound 30min after stirring；
2. by above-mentioned solution at 160 DEG C hydro-thermal reaction 10h, after being cooled to room temperature, by the precipitation deionized water of generation
Cleaned 7 times with ethanol alternating centrifugal, then dried at 80 DEG C, calcine 2h at 500 DEG C again afterwards, finally just obtained ZnO
Hollow bouquet and CdO nano-particles reinforcement nano materials；
3. by the hollow bouquets of ZnO and CdO nano-particles reinforcements nano material and deionized water in mass ratio 5:1 mixing, and
Grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two ring-types, phases with brush
Mutually the aluminium oxide ceramics pipe surface of parallel and separate gold electrode, forms the sensitive material film of 30 μ m-thicks, and makes sensitivity
Material is completely covered annular gold electrode；Wherein, the length of earthenware is 4mm, and external diameter is 1.2mm, and internal diameter is 0.8mm, 2 annulars
The width of gold electrode is 0.8mm, and two electrode spacings are 1.8mm, two platinum filaments are connected with each gold electrode and make pin, platinum filament
Length be 9mm；
4. the alumina ceramic tube that sensitive material will be scribbled toasts 30min at 90 DEG C, after after sensitive material drying, oxidation
Aluminium earthenware calcines 2h in being put into Muffle furnace at 400 DEG C；Then a resistance value is 30 Ω, the nickel chromium triangle that the number of turn is 40 circles is closed
Golden heating coil is passed as heater strip from ceramic tube inside, and finally above-mentioned device is welded according to heater-type gas sensor
And encapsulation, just obtain the heater-type alcohol gas based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and sensed
Device.
Embodiment 2：
With Cd:Zn mol ratios 0.88:100 (this ratio is within the raw material dosage scope described in the content of the inventionIt is
) the hollow bouquets of ZnO of preparation make alcohol gas sensor, its specific making with CdO nano-particles reinforcements nano material
Process is as follows：
1. first by the hollow bouquet powder of 30mg ZnO, the Cd (NO of 0.006g3)2·4H2O (four nitric hydrate cadmiums),
The CH of 0.012g4N2S (thiocarbamide) is added sequentially to 30mL DMF, is kept stirring for until it is all after dissolving, then by 300 μ L isopropyls
Alcohol is added in above-mentioned solution, continues to stir 10min, ultrasound 30min after stirring；
2. by above-mentioned solution at 160 DEG C hydro-thermal reaction 10h, after being cooled to room temperature, by the precipitation deionized water of generation
Cleaned 7 times with ethanol alternating centrifugal, then dried at 80 DEG C, calcine 2h at 500 DEG C again afterwards, finally just obtained ZnO
Hollow bouquet and CdO nano-particles reinforcement nano materials；
3. by the hollow bouquets of ZnO and CdO nano-particles reinforcements nano material and deionized water in mass ratio 5:1 mixing, and
Grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two ring-types, phases with brush
Mutually the aluminium oxide ceramics pipe surface of parallel and separate gold electrode, forms the sensitive material film of 30 μ m-thicks, and makes sensitivity
Material is completely covered annular gold electrode；Wherein, the length of earthenware is 4mm, and external diameter is 1.2mm, and internal diameter is 0.8mm, 2 annulars
The width of gold electrode is 0.8mm, and two electrode spacings are 1.8mm, two platinum filaments are connected with each gold electrode and make pin, platinum filament
Length be 9mm；
4. the alumina ceramic tube that sensitive material will be scribbled toasts 30min at 90 DEG C, after after sensitive material drying, oxidation
Aluminium earthenware calcines 2h in being put into Muffle furnace at 400 DEG C；Then a resistance value is 30 Ω, the nickel chromium triangle that the number of turn is 40 circles is closed
Golden heating coil is passed as heater strip from ceramic tube inside, and finally above-mentioned device is welded according to heater-type gas sensor
And encapsulation, just obtain the heater-type alcohol gas based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and sensed
Device.
Embodiment 3：
With Cd:Zn mol ratios 2.64:100 (this ratio is within the raw material dosage scope described in the content of the inventionIt is
) the hollow bouquets of ZnO of preparation make alcohol gas sensor, its specific making with CdO nano-particles reinforcements nano material
Process is as follows：
1. first by the hollow bouquet powder of 30mg ZnO, the Cd (NO of 0.012g3)2·4H2O (four nitric hydrate cadmiums),
The CH of 0.024g4N2S (thiocarbamide) is added sequentially to 30mL DMF, is kept stirring for until it is all after dissolving, then by 300 μ L isopropyls
Alcohol is added in above-mentioned solution, continues to stir 10min, ultrasound 30min after stirring；
2. by above-mentioned solution at 160 DEG C hydro-thermal reaction 10h, after being cooled to room temperature, by the precipitation deionized water of generation
Cleaned 7 times with ethanol alternating centrifugal, then dried at 80 DEG C, calcine 2h at 500 DEG C again afterwards, finally just obtained ZnO
Hollow bouquet and CdO nano-particles reinforcement nano materials；
3. by the hollow bouquets of ZnO and CdO nano-particles reinforcements nano material and deionized water in mass ratio 5:1 mixing, and
Grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two ring-types, phases with brush
Mutually the aluminium oxide ceramics pipe surface of parallel and separate gold electrode, forms the sensitive material film of 30 μ m-thicks, and makes sensitivity
Material is completely covered annular gold electrode；Wherein, the length of earthenware is 4mm, and external diameter is 1.2mm, and internal diameter is 0.8mm, 2 annulars
The width of gold electrode is 0.8mm, and two electrode spacings are 1.8mm, two platinum filaments are connected with each gold electrode and make pin, platinum filament
Length be 9mm；
4. the alumina ceramic tube that sensitive material will be scribbled toasts 30min at 90 DEG C, after after sensitive material drying, oxidation
Aluminium earthenware calcines 2h in being put into Muffle furnace at 400 DEG C；Then a resistance value is 30 Ω, the nickel chromium triangle that the number of turn is 40 circles is closed
Golden heating coil is passed as heater strip from ceramic tube inside, and finally above-mentioned device is welded according to heater-type gas sensor
And encapsulation, just obtain the heater-type alcohol gas sensor based on the hollow bouquet of CdO/ZnO heterojunction structures.
Embodiment 4：
With Cd:Zn mol ratios 4.4:100 (this ratio is within the raw material dosage scope described in the content of the invention) prepare
The hollow bouquets of ZnO and CdO nano-particles reinforcements nano material make alcohol gas sensor, its specific manufacturing process is such as
Under：
1. first by the hollow bouquet powder of 30mg ZnO, the Cd (NO of 0.024g3)2·4H2O (four nitric hydrate cadmiums),
The CH of 0.048g4N2S (thiocarbamide) is added sequentially to 30mL DMF, is kept stirring for until it is all after dissolving, then by 300 μ L isopropyls
Alcohol is added in above-mentioned solution, continues to stir 10min, ultrasound 30min after stirring；
2. by above-mentioned solution at 160 DEG C hydro-thermal reaction 10h, after being cooled to room temperature, by the precipitation deionized water of generation
Cleaned 7 times with ethanol alternating centrifugal, then dried at 80 DEG C, calcine 2h at 500 DEG C again afterwards, finally just obtained ZnO
Hollow bouquet and CdO nano-particles reinforcement nano materials；
3. by the hollow bouquets of ZnO and CdO nano-particles reinforcements nano material and deionized water in mass ratio 5:1 mixing, and
Grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two ring-types, phases with brush
Mutually the aluminium oxide ceramics pipe surface of parallel and separate gold electrode, forms the sensitive material film of 30 μ m-thicks, and makes sensitivity
Material is completely covered annular gold electrode；Wherein, the length of earthenware is 4mm, and external diameter is 1.2mm, and internal diameter is 0.8mm, 2 annulars
The width of gold electrode is 0.8mm, and two electrode spacings are 1.8mm, two platinum filaments are connected with each gold electrode and make pin, platinum filament
Length be 9mm；
4. the alumina ceramic tube that sensitive material will be scribbled toasts 30min at 90 DEG C, after after sensitive material drying, oxidation
Aluminium earthenware calcines 2h in being put into Muffle furnace at 400 DEG C；Then a resistance value is 30 Ω, the nickel chromium triangle that the number of turn is 40 circles is closed
Golden heating coil is passed as heater strip from ceramic tube inside, and finally above-mentioned device is welded according to heater-type gas sensor
And encapsulation, just obtain the heater-type alcohol gas based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials and sensed
Device.
Claims (4)
1. a kind of alcohol gas sensor based on the hollow bouquets of ZnO Yu CdO nano-particles reinforcement nano materials, is heater-type gas
Body sensor, by outer surface with two ring-types, be parallel to each other and the alumina ceramic tube of gold electrode separate, nickel chromium triangle are closed
Golden heating coil, sensitive material coating composition；Nichrome heating coil passes through ceramic tube inside, is the normal work of sensor
Suitable temperature is provided, it is characterised in that：Sensitive material is the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials, and by
Following steps are prepared,
(1) first by the Zn (CH of 0.4~0.8g3COO)2·2H2O, the glycine of 0.4~0.8g, the Na of 0.4~0.8g2SO4·
10H2O is added sequentially in the mixed solvent of 10~15mL deionized waters and 10~15mL ethanol, is added after 10~20min of stirring
The NaOH of 0.4~0.8g, then stirring is until well mixed；
(2) above-mentioned solution is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, then by stainless steel cauldron 160~
10~14h of hydro-thermal reaction at 180 DEG C, after being cooled to room temperature, the precipitation deionized water and ethanol alternating centrifugal that will be collected into are clear
Wash 5~7 times, then dried at 70~90 DEG C, calcine 1~2h at 400~500 DEG C again afterwards, obtain the hollow bouquet powder of ZnO
End, its a diameter of 2~3 μm, the hollow bouquet hetero-junctions of ZnO is formed by nanometer sheet is interspersed, the thickness of its part nanometer sheet
It is 60~70nm；
(3) again by the hollow bouquet powder of the ZnO of 0.03~0.05g, the Cd (NO of 0.003~0.024g3)2·4H2O and 0.0108
The CH of~0.0216g4N2S is added sequentially in the DMF of the isopropanol containing 200~400 μ L and 25~30mL, and stirring 10~
20~30min of ultrasound after 20min is until form homogeneous mixture solotion；
(4) solution obtained in step (3) is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, then by stainless steel reaction
Kettle 8~12h of hydro-thermal reaction at 150~170 DEG C, after being cooled to room temperature, the precipitation deionized water and ethanol that will be collected into are handed over
For eccentric cleaning 5~7 times, then dried at 70~90 DEG C, calcine 1~2h at 450~550 DEG C again afterwards, obtain ZnO empty
Disc flower ball and CdO nano-particles reinforcement nano material powder；Wherein a diameter of 9~12nm of CdO nano particles.
2. a kind of alcohol gas based on the hollow bouquets of ZnO Yu CdO nano-particles reinforcement nano materials as claimed in claim 1
Sensor, it is characterised in that：The length of earthenware is 4~4.5mm, and external diameter is 1.2~1.4mm, and internal diameter is 0.8~0.9mm, 2
The width of individual annular gold electrode is 0.8~0.9mm, and two electrode spacings are 1.8~2.0mm；Two are connected with each gold electrode
Root platinum filament makees pin, and the length of platinum filament is 9~10mm, and resistance is 38~40 Ω；The resistance of nichrome heating coil be 20~
30 Ω, the number of turn are 30~40 circles.
3. a kind of alcohol gas based on the hollow bouquets of ZnO Yu CdO nano-particles reinforcement nano materials as claimed in claim 1
Sensor, it is characterised in that：The thickness of sensitive material coating is 20~30 μm.
4. a kind of alcohol gas based on the hollow bouquets of ZnO and CdO nano-particles reinforcement nano materials described in claim 1 are passed
The preparation method of sensor, its step is as follows：
(1) by the hollow bouquets of ZnO and CdO nano-particles reinforcement nano material powder and deionized water in mass ratio 3~5：1 mixes
Close, and grinding forms pasty slurry, and above-mentioned slurry then is uniformly coated on into commercially available outer surface with two rings with brush
Shape, be parallel to each other and gold electrode separate aluminium oxide ceramics pipe surface, and make sensitive material that annular gold electricity is completely covered
Pole；
(2) alumina ceramic tube that will scribble sensitive material toasts 20~30min at being 80 DEG C~100 DEG C in temperature, treats sensitivity
After material is dried, alumina ceramic tube is calcined 2~5h at 400~500 DEG C；Then by nichrome heating coil from ceramics
Passed inside pipe as heater strip, finally above-mentioned device is welded and encapsulated according to heater-type gas sensor, just obtained
Heater-type alcohol gas sensor based on the hollow bouquets of ZnO Yu CdO nano-particles reinforcement nano materials.
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