CN105181896B - A kind of gas sensitive and its element and preparation method for detecting acetone gas - Google Patents
A kind of gas sensitive and its element and preparation method for detecting acetone gas Download PDFInfo
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- CN105181896B CN105181896B CN201510550566.6A CN201510550566A CN105181896B CN 105181896 B CN105181896 B CN 105181896B CN 201510550566 A CN201510550566 A CN 201510550566A CN 105181896 B CN105181896 B CN 105181896B
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Abstract
The invention provides a kind of gas sensitive for detecting acetone gas, constituted by ZnO nano piece and graphene oxide are compound, the mass percent that graphene oxide accounts for gas sensitive is 5 ~ 20%.Present invention also offers the preparation method of above-mentioned gas sensitive, ZnO nano piece is first prepared, ZnO is obtained by the method for solid-phase grinding：Graphite quality ratio is 1：1 mixing material, then to adding P in mixing material2O5, obtain ZnO nano piece；Graphene oxide solution is prepared again, and the graphene oxide solution and ZnO nano piece that will be prepared mix, and the gas sensitive for detecting acetone gas is dried to obtain after being well mixed.Present invention also offers the gas sensor for detecting acetone gas, gas sensitive is coated on semiconductor element, the gas sensor containing ZnO nano piece and graphene oxide composite material is obtained.Gas sensor of the invention is high to acetone gas sensitivity, and, response recovery time good to interference gas-selectively is short.
Description
Technical field
The invention belongs to Metal Oxide Semiconductor Gas Sensing Element Technology field, and in particular to one kind is for detecting acetone gas
The gas sensitive and its element and preparation method of body.
Technical background
Acetone is a kind of reagent being widely used in industry and laboratory, but is easy to volatilize at room temperature.In acetone
Poison is mainly shown as the anesthetic effect of Central nervous system, weak, nauseous, headache, dizzy, emotional occurs.Severe one occurs
Vomiting, out of breath, spasm, or even stupor.It is irritant to eye, nose, larynx.After oral, first there is lip, throat to have burn feeling, after go out
Existing dry, vomiting, stupor, acid poisoning and ketosis.The Long Term Contact product occur dizziness, burning sensation, pharyngitis, bronchitis, it is weak,
It is emotional etc..The prolonged and repeated contact of skin can cause dermatitis.Meanwhile, acetone is extremely inflammable, has excitant.Suck excessive acetone meeting
Cause headache, fatigue, even go into a coma, damage is caused to nervous system.In addition, when insulin can not be glucose normal transmission
During to cell, human body will be forced to use the fat of storage as main energy sources while producing acetone gas.Therefore, diabetes
Exist between acetone and be closely connected.Abnormal acetone concentration in the exhaled gas of people can be as the biology of detection diabetes
Marker substances.Therefore, detection acetone is most important to the life security of environment and people.Exploitation has high selectivity to acetone,
Sensitivity gas sensor high has important practical significance.
Although some existing gas sensors can be used for detecting acetone, major part detection essence currently on the market
Degree and selectivity are relatively low, it is impossible to meet the demand of each side.One good acetone sensor not only needs good sensitive
Degree and stability, but also need to have good selectivity, the height of selectivity is the weight of tailored version gas sensor performance evaluation
Want parameter.In sum, the portable acetone gas sensor of high, the selective good, stable performance of exploitation sensitivity has huge
Economic worth and social value.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of air-sensitive material for detecting acetone gas
Material and its element and preparation method, described this gas sensitive and its element and preparation method solution for detecting acetone gas
Acetone sensor accuracy of detection of the prior art of having determined and the relatively low technical problem of selectivity.
The invention provides a kind of gas sensitive for detecting acetone gas, it is made up of ZnO nano piece, described
Doped with graphene oxide in ZnO nano piece, described graphene oxide account for the mass percent of described gas sensitive for 5 ~
20%。
Further, the mass percent that described graphene oxide accounts for described gas sensitive is 10%.
Present invention also offers a kind of above-mentioned preparation method for detecting the gas sensitive of acetone gas stated, including such as
Lower step：
1) ZnO particle, graphite are weighed, described ZnO and graphite quality ratio are 1：1, it is obtained by the method for solid-phase grinding
The mixing material of ZnO and graphite, then to adding P in mixing material2O5, described P2O5Quality be the mixing material quality
1-10 %, mixing material is well mixed, obtain ZnO nano piece prepare needed for raw material；
2) above-mentioned raw material are weighed, is placed in a reaction vessel, be 1 nm in the plated surface thickness of above-mentioned raw material
Au, by silicon chip or 111 Al that the direction of growth is 1002O3Substrate is placed on the center of reaction vessel, by reaction vessel
It is placed in CVD tube furnaces, is warming up to 900 ~ 1100 DEG C, the heating-up time is 15 ~ 25 min；Holding temperature is 900 ~ 1100 DEG C, is protected
The warm time is 3 ~ 8 min；Then Temperature fall obtains ZnO nano piece；
3) a step of improved Hummers method of use prepares graphite oxide；
4) graphite oxide is weighed, ethanol is added, described graphite oxide and the mass volume ratio of ethanol is 1g：100~
200mL, ultrasound obtains graphene oxide solution in being put into ultrasonic wave；
5) the ZnO nano piece and graphene oxide solution mixing for obtaining will be produced, the quality of described graphene oxide is
The 5 ~ 20% of ZnO nano piece and graphene oxide quality sum, 50 ~ 70 DEG C of dryings 1 ~ 3 hour, that is, obtain for detecting acetone gas
The gas sensitive of body.
Specifically, step 4）In, ultrasonic time is 1 ~ 3 hour.
Present invention also offers a kind of gas sensor for detecting acetone gas, it is made up of a semiconductor element,
Described semiconductor component surfaces coat above-mentioned gas sensitive.
Further, described semiconductor element is aluminium oxide ceramics pipe surface or micro-hotplate.
Present invention also offers a kind of above-mentioned preparation method for detecting the gas sensor of acetone gas, in air-sensitive material
Ethanol is added in material, the described quality of gas sensitive and the mass volume ratio of ethanol is 1g：10 ~ 15mL, gas sensitive is applied
Apply on semiconductor element, gas sensor is welded by heater-type semiconductor gas sensor manufacture craft, for detecting third
The gas sensor of ketone gas.
Gas sensor of the invention obtained have it is high to acetone gas sensitivity, it is good to interference gas-selectively, respond it is extensive
The multiple advantage that the time is short, detection range is wide.Good acetone gas detectability makes the detection of its acetone gas, family expenses or medical treatment
There is huge application space with aspects such as diabetes detection sensors.
Acetone gas sensor the key technical indexes of the invention is as follows：
1. detection range：Ppm ~ 500 ppm of gas concentration 1；
2. element manipulation temperature： 200~260 ℃；
3. detection sensitivity (Ra/Rg)：100 ppm acetone sensitivity are 35.8；
4. selective：To 100 ppm benzene, methyl alcohol, formaldehyde, ammonia, CO, H25 are less than Deng sensitivity；
5. element responds time：Less than 13s；
6. element recovery time：Less than 7s.
Brief description of the drawings
Fig. 1 is 10 wt% graphene oxides and ZnO nano piece composite prepared by the inventive method, and the ZnO of P doping receives
Rice piece and the tri- kinds of x-ray diffraction patterns of material of ZnO without P doping.
Fig. 2 is 10 wt% graphene oxides and ZnO nano piece composite prepared by the inventive method, and the ZnO of P doping receives
Rice piece and the tri- kinds of scanning electron microscope diagrams of material of ZnO without P doping.
Fig. 3 is the 10 wt% graphene oxides and P doping zinc oxide nanometer sheet composites for preparing in the process of the present invention, P doping
ZnO nano piece and the tri- kinds of materials of ZnO without P doping to the response recovery curve of 100 ppm acetone.
Fig. 4 is 10 wt% graphene oxides and P doping zinc oxide nanometer sheet composites, ZnO nano piece and mixed without P that P adulterates
Miscellaneous tri- kinds of materials of ZnO are relatively schemed to the selectivity ratios of the various gases of 100 ppm.As seen from the figure 10 wt% graphene oxides and
ZnO nano piece composite has high selectivity and high sensitivity to acetone gas.
Fig. 5 is 0 wt%, 5 wt%, 10 wt%, 15 wt% and 20 for the mass ratio of composite shared by graphene oxide
Under the conditions of wt%, the selectivity ratios to the various gases of 100 ppm are relatively schemed.
Specific embodiment
Hereinafter with example, the invention will be further described, but not limited to this.
Embodiment 1
Acetone gas sensor making step：
A. with ZnO particle, graphite and P2O5It is raw material, it is ZnO that mass ratio is obtained：Graphite=1：1 mixing material, then to
P is added in material2O5, make its quality proportion for 2.5 wt%, mixing material is placed in mortar and is fully ground, mix it
Uniformly, obtain producing the raw material of ZnO nano piece.
B. above-mentioned material is weighed into 0.8 g, is poured into porcelain boat, fully polished with surface of the key by material in porcelain boat,
It is by plated surface Au, the direction of growth（100）Silicon chip be placed on the center of porcelain boat, porcelain boat is placed on CVD tube furnaces afterwards
In, it is 1000 DEG C to set warming temperature, and the heating-up time is 20 min；Holding temperature is 1000 DEG C, and soaking time is 5 min；
Then room temperature is freely down to, final ZnO nano piece is obtained.
C. the graphite oxide of a certain amount of 0.5g is taken, 50 ~ 100mL ethanol is added, ultrasonic 1 h obtains oxygen in being put into ultrasonic wave
Graphite alkene solution.
Specifically, described graphite oxide is prepared by improved Hummers methods, specific method is as follows：
The 30 mL concentrated sulfuric acids, 2.5 g potassium peroxydisulfates are added after being stirred until homogeneous in 2.5 g phosphorus pentoxides addition beaker
5 g native graphites, continue to stir half an hour.This process is the preliminary oxidation process to native graphite.Pre-oxidized to the first step
Add 2.5 g sodium nitrate, the 85 mL concentrated sulfuric acids that beaker is placed in the container for filling mixture of ice and water in graphite, use electric stirring
Device stirs 10 min, then 15 g potassium permanganate of uniform slow addition, continues to stir 2 h, is well mixed it；To fill anti-
Answer in the water bath with thermostatic control of 35 DEG C of beaker immigration of thing, continue to stir 50 min；It is slow be homogeneously added into 230 mL, 35 DEG C go
Ionized water, continues to stir 1 h after then in the 98 DEG C of waters bath with thermostatic control of large beaker dislocation, reaching design temperature, and now liquid is presented
Go out brown；After the completion of reaction, to 500 mL deionized waters and a certain amount of 30% hydrogenperoxide steam generator is added in beaker, to remove
Remove excessive potassium permanganate.Stirred with glass bar, supernatant liquor is poured out after centrifugation, add 5% hydrochloric acid solution washing number
It is secondary, until supernatant liquor is in neutrality；The sample that will have been washed dries 24 h in being put into 40 DEG C of vacuum drying chamber, is aoxidized
Graphite.
D. graphene oxide solution is impregnated into ZnO nano piece, is mixed according to 10 wt% of gross mass shared by graphene oxide
Conjunction is poured into mortar, adds ethanol, the mass volume ratio of the quality sum and ethanol of ZnO nano piece and graphene oxide mixture
It is 1g：10mL.After being fully ground uniformly, material is coated on Silica tubes, by heater-type semiconductor gas sensor
Manufacture craft is welded to gas sensor, and the gas sensor of ZnO nano piece and graphene oxide composite material is obtained.
Products therefrom image is characterized by X-ray diffraction.Referring to Fig. 1, the diffraction maximum in Fig. 1 is mainly six
Square wurtzite-type ZnO（JCPDS 361451）, the peak of its GO is apparent.Its microscopic appearance is entered by SEM
Row is characterized.Fig. 2 a show no addition P in raw material2O5When only obtain tri-star dress nano material.When adding P in raw material2O5
Afterwards, can be seen that material is nanometer chip architecture from Fig. 2 b.Fig. 2 c and 2d be ZnO nano piece and graphene oxide it is compound after SEM
Figure.The graphene oxide that flexibility is will become apparent from from figure has wrapped up rigid ZnO nano piece.Air-sensitive performance passes through static distribution
Method, in the quick performance test of enterprising promoting the circulation of qi of CGS-8 Testing system of gas-sensor built.Referring to Fig. 3, element is to 100 ppm acetone
Response recovers quickly and sensitivity is higher.Referring to Fig. 4, to the selectivity of acetone after ZnO nano piece and graphene oxide are compound
Improve a lot.Referring to Fig. 5, the mass ratio of material shared by graphene oxide is 10 wt% and ZnO nano piece composite pair
Acetone gas have high selectivity and high sensitivity.
Embodiment 2
The present embodiment is essentially identical with embodiment one, except that：Produced in a steps and be not added with ZnO nano piece step
P2O5。
Embodiment 3
This embodiment is essentially identical with example one, except that：Graphene oxide is added without in d steps.
Embodiment 4
This embodiment is essentially identical with example one, except that：Composite wood shared by graphene oxide in d steps
The mass ratio of material is 5%.
Embodiment 5
This embodiment is essentially identical with example one, except that：Composite wood shared by graphene oxide in d steps
The mass ratio of material is 15%.
Embodiment 6
This embodiment is essentially identical with example one, except that：Composite shared by graphene oxide in d steps
Mass ratio be 20%.
Claims (1)
1. a kind of preparation method for detecting the gas sensitive of acetone gas, it is characterised in that comprise the following steps：
1）ZnO particle, graphite are weighed, described ZnO and graphite quality ratio are 1：1, by the method for solid-phase grinding be obtained ZnO and
The mixing material of graphite, then to adding P in mixing material2O5, described P2O5Quality be the mixing material quality 1-10
%, mixing material is well mixed, and obtains the raw material needed for prepared by ZnO nano piece；
2）Above-mentioned raw material are weighed, is placed in a reaction vessel, in the Au that the plated surface thickness of above-mentioned raw material is 1 nm,
By silicon chip or 111 Al that the direction of growth is 1002O3Substrate is placed on the center of reaction vessel, and reaction vessel is placed on
In CVD tube furnaces, 900 ~ 1100 DEG C are warming up to, the heating-up time is 15 ~ 25 min；Holding temperature is 900 ~ 1100 DEG C, during insulation
Between be 3 ~ 8 min；Then Temperature fall obtains ZnO nano piece；
3）The step of one improved Hummers method of use prepares graphite oxide；
4）Graphite oxide is weighed, ethanol is added, described graphite oxide and the mass volume ratio of ethanol are 1g：100 ~ 200mL, puts
Ultrasound obtains graphene oxide solution in entering ultrasonic wave；
5）The ZnO nano piece that obtains and graphene oxide solution mixing will be produced, the quality of described graphene oxide is received for ZnO
5 ~ 20%, 50 ~ 70 DEG C of dryings of rice piece and graphene oxide quality sum 1 ~ 3 hour, that is, obtain for detecting acetone gas
Gas sensitive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106053549B (en) * | 2016-05-30 | 2019-02-19 | 安徽工业大学 | It is a kind of for detecting the gas sensitive of low concentration acetone |
| CN108572197A (en) * | 2018-04-17 | 2018-09-25 | 上海理工大学 | A kind of gas sensitive and its preparation method and application that acetone detection is used |
| CN110672671B (en) * | 2019-10-18 | 2022-04-01 | 上海理工大学 | Acetone sensitive material and sensitive element and preparation method thereof |
| CN114408962A (en) * | 2021-12-23 | 2022-04-29 | 海南聚能科技创新研究院有限公司 | Preparation method and application of rGO modified zinc oxide-based sensing material |
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