CN109668937A - A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure - Google Patents
A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure Download PDFInfo
- Publication number
- CN109668937A CN109668937A CN201811522769.4A CN201811522769A CN109668937A CN 109668937 A CN109668937 A CN 109668937A CN 201811522769 A CN201811522769 A CN 201811522769A CN 109668937 A CN109668937 A CN 109668937A
- Authority
- CN
- China
- Prior art keywords
- amorphous carbon
- composite nano
- nano fiber
- graphene
- cobaltosic oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention belongs to sensor technical fields, provide the composite nano fiber ammonia gas sensor and its preparation process of a kind of amorphous carbon-graphene-cobaltosic oxide package structure.A kind of amorphous carbon-graphene-cobaltosic oxide package structure composite nano fiber ammonia gas sensor of the present invention, including gas sensitive and substrate, the gas sensitive is coated uniformly on the substrate surface, the gas sensitive ingredient includes amorphous carbon, reproducibility graphene package cobaltosic oxide composite nano fiber, and the gas sensitive coating thickness is 0.4~0.5 μm.Ammonia gas sensor of the invention is to NH3The response performance of gas has better choice, sensitivity, stability and lower operating temperature.
Description
Technical field
The invention belongs to sensor technical fields, and in particular to a kind of amorphous carbon-graphene-cobaltosic oxide package structure
Composite nano fiber ammonia gas sensor and its preparation process.
Background technique
Nowadays, environment is monitored by detection VOC gas and disease has caused more and more to pay close attention to.Numerous
In VOC gas, ammonia is very big to the harm of human body, especially irritant to skin and eyes.It is supervised in the environment of certain occasions
In survey, the detection of ammonia is also particularly significant, for example, farm, sewage treatment plant, pharmaceutical factory, agricultural greenhouse greenhouse, chicken farm with
And manufacturing enterprise of ammonia etc..In addition to this, ammonia is also important the biomarker of diagnosis of nephropathy, ammonia in Healthy People breathing
0.03~0.7ppm of concentration of gas, nephrotic are 0.8~14.7ppm.Due to there are these demands, studied in recent years about ammonia
Chemical sensor it is more and more, for example considerable researcher is dedicated to the ammonia gas sensor based on metal oxide, such as
ZnO, SnO2, TiO2And Co3O4Often respond higher Deng, these sensors, cost is relatively low but needs higher work temperature
Degree, selectivity are bad.How to improve performance becomes the big hot issue of ammonia gas sensor those skilled in the art.
As the Schedin etc. of Univ Manchester UK since 2004 is recently reported graphene for first theory of evolution
The potential application of sensor causes people and greatly pays close attention to.They are (big with the sensor detection ammonia molecule based on graphene
General 1ppm), the response time is a few minutes, restores to need probably a few minutes after 150 degree of annealing in a vacuum to complete.Based on carbon material
Including carbon nanotube, amorphous carbon, such as graphene oxide of the Graphene derivative with surface functional group (GO) or reproducibility graphite
Alkene (rGO), compound sensor starts largely to be studied with metal oxide, can effectively improve and aoxidize for metal merely
The gas-sensitive property of object sensor is primarily due to compound and combines available characteristic different in its composition, Lai Gaishan compound
Machinery, chemically and electrically characteristic.Country etc. has synthesized carbon nanotube and the nanosphere hetero-junctions of ZnO, to 20ppm ammonia
Response is higher, and recovery time is general 10 minutes longer.
Therefore, it is simple to prepare a kind of processing step, it is at low cost and to NH3Selectivity is high, operating temperature easily reaches, surely
The ammonia gas sensor qualitative, restorability is strong and response recovery time is short becomes those skilled in the art's technology urgently to be resolved
Problem.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of couple of NH3Fast response time, stability
By force, the composite Nano that can effectively, accurately detect a kind of amorphous carbon-graphene-cobaltosic oxide package structure of ammonia level is fine
Tie up ammonia gas sensor and preparation method thereof.
Technical solution of the present invention:
A kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure, including air-sensitive
Material and substrate, gas sensitive are coated uniformly on substrate surface, and gas sensitive includes amorphous carbon and reproducibility graphene package four
Co 3 O composite nano fiber, gas sensitive coating thickness are 0.4~0.5 μm.
Amorphous carbon and reproducibility graphene wrap up cobaltosic oxide composite nano fiber, amorphous carbon and reproducibility graphite oxide
Alkene is wrapped on cobaltosic oxide, and the mass fraction that amorphous carbon accounts for composite nano fiber is 0.1%, and reproducibility graphene oxide accounts for
The mass fraction of composite nano fiber is 1%.
Amorphous carbon-the graphene-cobaltosic oxide package structure composite nano fiber average diameter is 150nm-
200nm。
The cobaltosic oxide is in granular form, average grain diameter 20nm.
The substrate is Si substrate or Al with Au electrode2O3Substrate.
A kind of preparation work of the composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure
Skill, comprising the following steps:
Step 1 prepares graphene oxide dispersion: the graphene oxide of 1 mass parts is distributed to the two of 2~3 mass parts
In methylformamide, after ultrasonic machine ultrasound, uniform graphene oxide dispersion is obtained；
Step 2 prepares the mixed liquor containing cobalt nitrate: by the Co (NO of 1 mass parts3)2·6H2O is dissolved into 1 mass parts
Ethyl alcohol in obtain solution a, the polyvinylpyrrolidone of 1 mass parts is dissolved into the ethyl alcohol of 1 mass parts and obtains solution b, will
Solution a is mixed with solution b according to volume ratio 1:1, is mixed by magnetic agitation to clarification, and the mixing containing cobalt nitrate is obtained
Liquid；
Step 3 prepares electrostatic spinning precursor liquid: the 1 mass parts graphene oxide dispersion that step 1 is obtained is added to
In the mixed liquor for the 1 mass parts cobalt nitrate that step 2 obtains, electrostatic spinning precursor liquid is obtained by magnetic agitation；
Step 4 prepares amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber:
Electrostatic spinning precursor liquid prepared by step 3 is fitted into the plastic injector with syringe needle, syringe needle is connected in 15kV-25kV direct current
On voltage, the feed speed of pump control electrostatic spinning precursor liquid is promoted by syringe, aluminium-foil paper is placed at syringe needle direction
In grounding electrode plate, the nanofiber that electrostatic spinning generates is collected；The nanofiber is first sintered in Ar environment and is prepared into
Amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber；
Step 5 regulates and controls amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber
Conductance: composite nano fiber prepared by step 4 is being contained into O2Ar environment under carry out different time processing, had
The amorphous carbon of different conductances-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber；
Step 6 prepares a kind of composite nano fiber ammonia sensing of amorphous carbon-graphene-cobaltosic oxide package structure
Device: the amorphous carbon for taking step 5 to obtain-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber dispersion
Into deionized water, the dispersion liquid of 8mg/mL~10mg/mL is formed, by dispersion to substrate surface, obtains ammonia after dry
Gas sensor.
Ultrasonic machine power in step 1 is 250W, and ultrasonic time is 0.5h~3h.
Magnetic agitation time in step 3 is 8h~for 24 hours.
Pump is promoted so that the feed speed of the electrostatic spinning precursor liquid is 0.1-0.5ml/ by syringe in step 4
h。
The stainless steel syringe needle that syringe needle described in step 4 is No. N7, the aluminium-foil paper are placed on what the stainless steel syringe needle was directed toward
At the position of 10-18cm.
First 400 DEG C~600 DEG C sintering 3 hours in Ar environment of nanofiber described in step 4, then in Ar environment
It is sintered 30 minutes at 750 DEG C~850 DEG C.
It is 2-8%O that nanofiber described in step 5, which contains volume fraction,2Ar environment under, 100-450 DEG C handle
50s-600s。
Coating method in step 6 includes spraying, roller coating or dipping.
Drying condition in step 6 is dry 2h~10h at 60 DEG C~100 DEG C.
Beneficial effects of the present invention:
(1) present invention obtains the Nanowire of the compositions such as graphene oxide and the nitrate precursor of Co using method of electrostatic spinning
Dimension, can prepare the nanofiber of pattern and structure-controllable, while it also has that equipment investment is small, process flow is simply excellent
Point.
(2) present invention obtains the Nanowire of the compositions such as graphene oxide and the nitrate precursor of Co using method of electrostatic spinning
Dimension, by realizing that amorphous carbon-redox graphene wraps up Co in Ar environment sintering process3O4Nanofiber, acquisition have packet
Amorphous carbon-redox graphene and the cobaltosic oxide composite nano fiber chemical property for wrapping up in structure be stable, to NH3Air-sensitive is special
Property is good.
(3) reduction of graphene oxide, it is compound with realization amorphous carbon-redox graphene package cobaltosic oxide, with
And the regulation of compound conductance in situ simultaneously can be completed, preparation step is few and technique is simpler.
(4) gas sensitive of ammonia gas sensor of the invention is amorphous carbon-four oxidation three of reproducibility graphene oxide package
Cobalt composite nanometer fiber, the gas sensitive are shown to NH3The better sensitivity of the response performance of gas, stability and faster
Response and the performances such as resume speed.
Detailed description of the invention
Fig. 1 is amorphous carbon of the present invention-reproducibility graphene oxide package cobaltosic oxide composite nano fiber X-ray diffraction
Figure gives amorphous carbon-reproducibility graphene oxide package cobaltosic oxide composite nano fiber X-ray diffraction of preparation
Figure, prepared nanofiber contain Co3O4。
Fig. 2 is amorphous carbon of the present invention-reproducibility graphene oxide package cobaltosic oxide composite nano fiber Raman map,
The amorphous carbon of preparation-reproducibility graphene oxide package cobaltosic oxide composite nano fiber Raman map, prepared is non-
Brilliant carbon-reproducibility graphene oxide package cobaltosic oxide composite nano fiber has the peak D of typical reproducibility graphene, G
Peak, the peak 2D.
Fig. 3 is amorphous carbon of the present invention-reproducibility graphene oxide package cobaltosic oxide composite nano fiber difference amplification
The electronic transmission microscopic appearance figure of multiple, (a) under 0.5 μm of scale, (b) under 100nm scale, (c) under 50nm scale,
It is microcosmic to give prepared amorphous carbon-reproducibility graphene oxide package cobaltosic oxide composite nano fiber electronic transmission
Shape appearance figure, prepared amorphous carbon-reproducibility graphene oxide package cobaltosic oxide composite nano fiber, which has, typically to be received
Rice microstructure fiber.
Fig. 4 be ammonia gas sensor of the present invention in room temperature to about 5~100ppm NH3And the resistance of 50ppm repeatability becomes
Change response diagram.
Fig. 5 be ammonia gas sensor of the present invention in room temperature to several escaping gas and NH3Response comparison diagram.
When Fig. 6 is that amorphous carbon-reproducibility graphene oxide package cobaltosic oxide composite nano fiber does not carry out carbon removing
Electronic transmission microscopic appearance figure.
Specific embodiment
The present invention is described in detail below in conjunction with embodiment and attached drawing, it should be pointed out that described reality
It applies example and is intended merely to facilitate the understanding of the present invention, and do not play any restriction effect to it.
Embodiment 1
A kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure, including air-sensitive
Material and substrate, gas sensitive are coated uniformly on substrate surface, and gas sensitive coating thickness is 0.4 μm.Amorphous carbon, graphene packet
Wrap up in cobaltosic oxide composite nano fiber, including amorphous carbon, reproducibility graphene oxide and cobaltosic oxide, amorphous carbon, graphite
Alkene is wrapped on the cobaltosic oxide, and the mass fraction that amorphous carbon accounts for composite nano fiber is 0.1%, the reproducibility oxidation
The mass fraction that graphene accounts for composite nano fiber is 1%.Preparation method the following steps are included:
Step 1 prepares graphene oxide dispersion: the graphene oxide of 1 mass parts is distributed to the two of A~B mass parts
In methylformamide, behind in the ultrasonic machine in 250W ultrasound 1 hour, graphene oxide dispersion is obtained；
Step 2 prepares the mixed liquor containing cobalt nitrate: by the Co (NO of 0.5g3)2·6H2O is dissolved into the ethyl alcohol of 1ml
Solution a is obtained, 0.5g polyvinylpyrrolidone is dissolved into the ethyl alcohol of 1ml and obtains solution b, solution a and solution b are passed through into magnetic
Power is stirred to clarification, obtains the mixed liquor containing cobalt nitrate；
Step 3 prepares electrostatic spinning precursor liquid: 1 mass parts graphene dispersing solution is added to the mixing containing cobalt nitrate
In liquid, electrostatic spinning precursor liquid was obtained by magnetic agitation 12 hours；
Step 4 prepares amorphous carbon-redox graphene and cobaltosic oxide composite nano fiber: is prepared by step 3
Electrostatic spinning precursor liquid be fitted into the plastic injector with N7 stainless steel syringe needle, syringe needle is connected in 19.5kV DC voltage
On, pump output electrostatic spinning precursor liquid is promoted by syringe, so that the output speed of the electrostatic spinning precursor liquid is
Aluminium-foil paper is placed at the position for the 13.5cm that the stainless steel syringe needle is directed toward by 0.2ml/h, collects the nanometer that electrostatic spinning generates
Fiber；By the nanofiber, first 550 DEG C of calcinings sintering in 3 hours in Ar environment, is then sintered 30 points in Ar environment at 800 DEG C
Clock.
Step 5 regulates and controls amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber
Conductance: composite nano fiber prepared by step 4 is being contained into O2The lower 410 DEG C of heat treatment 450s of Ar environment, obtain have electricity
Resistance is amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber gas sensing of 10M Ω
Device.
Step 6 prepares a kind of composite nano fiber ammonia sensing of amorphous carbon-graphene-cobaltosic oxide package structure
Device: the reproducibility graphene package cobaltosic oxide composite nano fiber 4mg for taking step 5 to obtain is dispersed in deionized water, shape
It at the dispersion liquid of 8mg/mL, takes 40 μ L dispersions to substrate surface, obtains ammonia gas sensor after 60 DEG C of dry 5h.
Embodiment 2
A kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure, including air-sensitive
Material and substrate, gas sensitive are coated uniformly on substrate surface, and gas sensitive coating thickness is 0.5 μm.Amorphous carbon, graphene packet
Wrap up in cobaltosic oxide composite nano fiber, including amorphous carbon, reproducibility graphene oxide and cobaltosic oxide, amorphous carbon, graphite
Alkene is wrapped on the cobaltosic oxide, and the mass fraction that amorphous carbon accounts for composite nano fiber is 1%, and the reproducibility aoxidizes stone
The mass fraction that black alkene accounts for composite nano fiber is 1%.Preparation method the following steps are included:
Step 1 prepares graphene oxide dispersion: the graphene oxide of 1 mass parts is distributed to the two of A~B mass parts
In methylformamide, behind in the ultrasonic machine in 250W ultrasound 1 hour, graphene oxide dispersion is obtained；
Step 2 prepares the mixed liquor containing cobalt nitrate: by the Co (NO of 0.5g3)2·6H2O is dissolved into the ethyl alcohol of 1ml
Solution a is obtained, 0.5g polyvinylpyrrolidone is dissolved into the ethyl alcohol of 1ml and obtains solution b, solution a and solution b are passed through into magnetic
Power is stirred to clarification, obtains the mixed liquor containing cobalt nitrate；
Step 3 prepares electrostatic spinning precursor liquid: 1 mass parts graphene dispersing solution is added to the mixing containing cobalt nitrate
In liquid, electrostatic spinning precursor liquid was obtained by magnetic agitation 12 hours；
Step 4 prepares amorphous carbon-redox graphene and cobaltosic oxide composite nano fiber: is prepared by step 3
Electrostatic spinning precursor liquid be fitted into the plastic injector with N7 stainless steel syringe needle, syringe needle is connected in 19.5kV DC voltage
On, pump output electrostatic spinning precursor liquid is promoted by syringe, so that the output speed of the electrostatic spinning precursor liquid is
Aluminium-foil paper is placed at the position for the 13.5cm that the stainless steel syringe needle is directed toward by 0.2ml/h, collects the nanometer that electrostatic spinning generates
Fiber；By the nanofiber, first 550 DEG C of calcinings sintering in 3 hours in Ar environment, is then sintered 30 points in Ar environment at 800 DEG C
Clock.
Step 5 regulates and controls amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber
Conductance: composite nano fiber prepared by step 4 is being contained into O2The lower 400 DEG C of heat treatment 350s of Ar environment, obtain have electricity
Resistance is amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber gas sensor of 1M Ω.
Step 6 prepares a kind of composite nano fiber ammonia sensing of amorphous carbon-graphene-cobaltosic oxide package structure
Device: the reproducibility graphene package cobaltosic oxide composite nano fiber 5mg for taking step 5 to obtain is dispersed in deionized water, shape
It at the dispersion liquid of 10mg/mL, takes 50 μ L dispersions to substrate surface, obtains ammonia gas sensor after 60 DEG C of dry 5h.
Embodiment 3
A kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure, including air-sensitive
Material and substrate, gas sensitive are coated uniformly on substrate surface, and gas sensitive coating thickness is 0.5 μm.Amorphous carbon, graphene packet
Wrap up in cobaltosic oxide composite nano fiber, including amorphous carbon, reproducibility graphene oxide and cobaltosic oxide, amorphous carbon, graphite
Alkene is wrapped on the cobaltosic oxide, and the mass fraction that amorphous carbon accounts for composite nano fiber is 2%, and the reproducibility aoxidizes stone
The mass fraction that black alkene accounts for composite nano fiber is 1%.Preparation method the following steps are included:
Step 1 prepares graphene oxide dispersion: the graphene oxide of 1 mass parts is distributed to the two of A~B mass parts
In methylformamide, behind in the ultrasonic machine in 250W ultrasound 1 hour, graphene oxide dispersion is obtained；
Step 2 prepares the mixed liquor containing cobalt nitrate: by the Co (NO of 0.5g3)2·6H2O is dissolved into the ethyl alcohol of 1ml
Solution a is obtained, 0.5g polyvinylpyrrolidone is dissolved into the ethyl alcohol of 1ml and obtains solution b, solution a and solution b are passed through into magnetic
Power is stirred to clarification, obtains the mixed liquor containing cobalt nitrate；
Step 3 prepares electrostatic spinning precursor liquid: 1 mass parts graphene dispersing solution is added to the mixing containing cobalt nitrate
In liquid, electrostatic spinning precursor liquid was obtained by magnetic agitation 12 hours；
Step 4 prepares amorphous carbon-redox graphene and cobaltosic oxide composite nano fiber: is prepared by step 3
Electrostatic spinning precursor liquid be fitted into the plastic injector with N7 stainless steel syringe needle, syringe needle is connected in 19.5kV DC voltage
On, pump output electrostatic spinning precursor liquid is promoted by syringe, so that the output speed of the electrostatic spinning precursor liquid is
Aluminium-foil paper is placed at the position for the 13.5cm that the stainless steel syringe needle is directed toward by 0.2ml/h, collects the nanometer that electrostatic spinning generates
Fiber；By the nanofiber, first 550 DEG C of calcinings sintering in 3 hours in Ar environment, is then sintered 30 points in Ar environment at 800 DEG C
Clock.
Step 5 regulates and controls amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber
Conductance: composite nano fiber prepared by step 4 is being contained into O2Ar environment under corona treatment 100s, obtain have electricity
Resistance is amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber gas sensing of 100k Ω
Device.
Step 6 prepares a kind of composite nano fiber ammonia sensing of amorphous carbon-graphene-cobaltosic oxide package structure
Device: the reproducibility graphene package cobaltosic oxide composite nano fiber 4.5mg for taking step 5 to obtain is dispersed in deionized water,
The dispersion liquid for forming 9mg/mL takes 45 μ L dispersions to substrate surface, obtains ammonia gas sensor after 60 DEG C of dry 5h.
Example IV ammonia gas sensor performance test
Sensor prepared by embodiment 1-3 is placed under an air atmosphere, operating temperature is room temperature, then introduces NH3Gas
Body molecule.In air and concentration NH is not being had to using air as background by multimeter measurement sensor3Resistance under atmosphere becomes
Change, the signal as sensor.It compares attached drawing by taking the ammonia gas sensor that embodiment 1 is prepared as an example to be illustrated, Fig. 4 gives
Prepared sensor is in the about 5~100ppm and NH of 50ppm three times3Under atmosphere, the situation of change of sensor resistance.
Sensor (about 4s) after several seconds, sensor resistance variation (i.e. inductive signal) reach the 90% of stationary value, relative to
Other same type of sensor, the speed of sensor signal is very fast, and detected value is accurate, and aerial recovery time is 3-
It is 5 minutes, fast than sensor (20 minutes) speed of previous graphene package cobaltosic oxide.Fig. 5 gives prepared biography
Sensor escaping gas several for ethyl alcohol, methanol etc. and NH3Response comparison at room temperature, it can be found that the sensor is to NH3
Response be other gases several times.
There are above embodiments it is found that the present invention obtains the nitrate precursor of graphene oxide and Co using method of electrostatic spinning
Etc. compositions nanofiber, by Ar environment sintering process realize amorphous carbon, redox graphene wrap up Co3O4Nanowire
Dimension, 550 DEG C of calcinings thermally decompose to generate cobaltosic oxide in 3 hours, calcine 30 minutes at 800 DEG C and be reduced to restore by graphene oxide
Property graphene oxide, is not oxidized by oxygen in Ar environmental protection carbon atom.Containing O2Ar environment under handle 10-1000s, can
To remove amorphous carbon, obtains the amorphous carbon with different resistance-reproducibility graphene oxide-cobaltosic oxide package structure and answer
Close nanofiber gas sensor.Amorphous carbon-the graphene and cobaltosic oxide composite Nano fibre with package structure obtained
Dimension, as a kind of gas sensitive main component of ammonia gas sensor of the present invention, what the present invention prepared is coated with the gas sensitive
Ammonia gas sensor to NH3The responsiveness of gas has the preferably property such as response, stability and faster response recovery time
Energy.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of range is protected, although explaining in detail referring to preferred embodiment to the present invention, those skilled in the art are answered
Work as understanding, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (9)
1. a kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure, feature exist
In amorphous carbon-graphene-cobaltosic oxide package structure composite nano fiber ammonia gas sensor includes gas sensitive
And substrate, gas sensitive are coated uniformly on substrate surface, gas sensitive includes four oxidation of amorphous carbon and reproducibility graphene package
Three cobalt composite nanometer fibers, gas sensitive coating thickness are 0.4~0.5 μm；
Amorphous carbon and reproducibility graphene wrap up cobaltosic oxide composite nano fiber, are amorphous carbon and reproducibility graphene oxide
It is wrapped on cobaltosic oxide, the mass fraction that amorphous carbon accounts for composite nano fiber is 0.1%, and reproducibility graphene oxide accounts for multiple
The mass fraction for closing nanofiber is 1%.
2. the composite nano fiber ammonia of amorphous carbon-graphene-cobaltosic oxide package structure according to claim 1 passes
Sensor, which is characterized in that the amorphous carbon-graphene-cobaltosic oxide package structure composite nano fiber average diameter is
150nm-200nm。
3. the composite nano fiber ammonia of amorphous carbon-graphene-cobaltosic oxide package structure according to claim 1 or 2
Gas sensor, which is characterized in that the cobaltosic oxide is in granular form, average grain diameter 20nm.
4. the composite nano fiber ammonia of amorphous carbon-graphene-cobaltosic oxide package structure according to claim 3 passes
Sensor, which is characterized in that the substrate is Si substrate or Al with Au electrode2O3Substrate.
5. a kind of preparation process of the composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure,
It is characterized in that, steps are as follows:
Step 1 prepares graphene oxide dispersion: the graphene oxide of 1 mass parts is distributed to the dimethyl of 2~3 mass parts
In formamide, after ultrasonic machine ultrasound, uniform graphene oxide dispersion is obtained；
Step 2 prepares the mixed liquor containing cobalt nitrate: by the Co (NO of 1 mass parts3)2·6H2O is dissolved into the ethyl alcohol of 1 mass parts
In obtain solution a, the polyvinylpyrrolidone of 1 mass parts is dissolved into the ethyl alcohol of 1 mass parts and obtains solution b, by solution a with
Solution b is mixed according to volume ratio 1:1, is mixed by magnetic agitation to clarification, and the mixed liquor containing cobalt nitrate is obtained；
Step 3 prepares electrostatic spinning precursor liquid: the 1 mass parts graphene oxide dispersion that step 1 is obtained is added to step
In the mixed liquor of two 1 obtained mass parts cobalt nitrates, electrostatic spinning precursor liquid is obtained by magnetic agitation；
Step 4 prepares amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber: will walk
The electrostatic spinning precursor liquid of rapid three preparation is fitted into the plastic injector with syringe needle, and syringe needle is connected in 15kV-25kV DC voltage
On, the feed speed of pump control electrostatic spinning precursor liquid is promoted by syringe, and aluminium-foil paper is placed on the ground connection at syringe needle direction
On electrode plate, the nanofiber that electrostatic spinning generates is collected；The nanofiber is first sintered in Ar environment and is prepared into amorphous
Carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber；
Step 5 regulates and controls amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber electricity
It leads: composite nano fiber prepared by step 4 is being contained into O2Ar environment under carry out different time processing, obtain have not
With amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber of conductance；
Step 6 prepares a kind of composite nano fiber ammonia gas sensor of amorphous carbon-graphene-cobaltosic oxide package structure:
The amorphous carbon for taking step 5 to obtain-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber is dispersed to
In deionized water, the dispersion liquid of 8mg/mL~10mg/mL is formed, by dispersion to substrate surface, obtains ammonia after dry
Sensor.
6. preparation process according to claim 5, which is characterized in that
In step 4 nanofiber first in Ar environment 400 DEG C~600 DEG C be sintered 3 hours, then 750 DEG C in Ar environment~
It is sintered 30 minutes at 850 DEG C.
7. preparation process according to claim 5 or 6, which is characterized in that
It is 2-8%O that nanofiber, which contains volume fraction, in step 52Ar environment under, 100s- is handled in 100-450 DEG C
600s。
8. preparation process according to claim 5 or 6, which is characterized in that
Ultrasonic machine power in step 1 is 250W, and ultrasonic time is 0.5h~3h；
Magnetic agitation time in step 3 is 8h~for 24 hours；
Pump is promoted so that the feed speed of the electrostatic spinning precursor liquid is 0.1-0.5ml/h by syringe in step 4；
The stainless steel syringe needle that syringe needle is No. N7 in step 4, aluminium-foil paper are placed on the position for the 10-18cm that the stainless steel syringe needle is directed toward
Set place；
Coating method in step 6 includes spraying, roller coating or dipping；
Drying condition in step 6 is dry 2h~10h at 60 DEG C~100 DEG C.
9. preparation process according to claim 7, which is characterized in that
Ultrasonic machine power in step 1 is 250W, and ultrasonic time is 0.5h~3h；
Magnetic agitation time in step 3 is 8h~for 24 hours；
Pump is promoted so that the feed speed of the electrostatic spinning precursor liquid is 0.1-0.5ml/h by syringe in step 4；
The stainless steel syringe needle that syringe needle is No. N7 in step 4, aluminium-foil paper are placed on the position for the 10-18cm that the stainless steel syringe needle is directed toward
Set place；
Coating method in step 6 includes spraying, roller coating or dipping；
Drying condition in step 6 is dry 2h~10h at 60 DEG C~100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811522769.4A CN109668937A (en) | 2018-12-13 | 2018-12-13 | A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811522769.4A CN109668937A (en) | 2018-12-13 | 2018-12-13 | A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109668937A true CN109668937A (en) | 2019-04-23 |
Family
ID=66145090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811522769.4A Pending CN109668937A (en) | 2018-12-13 | 2018-12-13 | A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109668937A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530928A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing graphene composite material loading amorphous carbon |
| CN104458826A (en) * | 2014-10-28 | 2015-03-25 | 大连理工大学 | Novel ammonia sensor and preparation technology thereof |
| US20150226699A1 (en) * | 2011-09-12 | 2015-08-13 | Nanoselect, Inc. | Carbon nanostructure sensor and method for biomolecule sensing |
| CN105842292A (en) * | 2016-03-28 | 2016-08-10 | 安徽芯核防务装备技术股份有限公司 | Semiconductor for normal-temperature gas-sensitive detection of hydrogen sulfide, and preparation and application thereof |
-
2018
- 2018-12-13 CN CN201811522769.4A patent/CN109668937A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530928A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing graphene composite material loading amorphous carbon |
| US20150226699A1 (en) * | 2011-09-12 | 2015-08-13 | Nanoselect, Inc. | Carbon nanostructure sensor and method for biomolecule sensing |
| CN104458826A (en) * | 2014-10-28 | 2015-03-25 | 大连理工大学 | Novel ammonia sensor and preparation technology thereof |
| CN105842292A (en) * | 2016-03-28 | 2016-08-10 | 安徽芯核防务装备技术股份有限公司 | Semiconductor for normal-temperature gas-sensitive detection of hydrogen sulfide, and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 岳根田: "基于异质结合导电聚合物对电极的染料敏化太阳能电池研究", 《中国博士学位论文全文数据库 工程科技II辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Highly sensitive ammonia sensors based on Ag-decorated WO 3 nanorods | |
| Wang et al. | Preparation of Pd/PdO loaded WO3 microspheres for H2S detection | |
| David et al. | Room temperature operatable high sensitive toluene gas sensor using chemiresistive Ag/Bi2O3 nanocomposite | |
| Hsu et al. | Rapid detection of low concentrations of H2S using CuO-doped ZnO nanofibers | |
| Zhao et al. | Porous CuO/SnO2 composite nanofibers fabricated by electrospinning and their H2S sensing properties | |
| Yu et al. | Electrospun ZnO nanotubes and its gas sensing applications | |
| Lee et al. | Conductometric ppb-level acetone gas sensor based on one-pot synthesized Au@ Co3O4 core-shell nanoparticles | |
| Sun et al. | Chemiresistive sensor arrays based on noncovalently functionalized multi-walled carbon nanotubes for ozone detection | |
| Tian et al. | Toluene sensing properties of porous Pd-loaded flower-like SnO2 microspheres | |
| Li et al. | ZrO2/ZnO nanocomposite materials for chemiresistive butanol sensors | |
| Ma et al. | Enhanced formaldehyde sensing performance at ppb level with Pt-doped nanosheet-assembled In2O3 hollow microspheres | |
| Zhang et al. | Preparation of Ce-doped SnO2 cuboids with enhanced 2-butanone sensing performance | |
| Xiaofeng et al. | Sensing performances to low concentration acetone for palladium doped LaFeO3 sensors | |
| Thangamani et al. | Hydrothermal synthesis of copper (׀׀) oxide-nanoparticles with highly enhanced BTEX gas sensing performance using chemiresistive sensor | |
| Ahmad et al. | Non-aqueous synthesis of hexagonal ZnO nanopyramids: gas sensing properties | |
| Zhai et al. | A highly sensitive gas sensor based on Pd-doped Fe 3 O 4 nanoparticles for volatile organic compounds detection | |
| Liu et al. | Highly sensitive and selective trimethylamine sensors based on WO3 nanorods decorated with Au nanoparticles | |
| CN111060560B (en) | Ru-WO3 nano material and preparation method and application thereof | |
| Chao et al. | Enhanced ammonia detection of gas sensors based on square-like tungsten oxide loaded by Pt nanoparticles | |
| Luo et al. | Role of cobalt in Co-ZnO nanoflower gas sensors for the detection of low concentration of VOCs | |
| Xuemei et al. | Fabrication of cubic pn heterojunction-like NiO/In 2 O 3 composite microparticles and their enhanced gas sensing characteristics | |
| Chi et al. | Synthesis of pristine In2O3/ZnO–In2O3 composited nanotubes and investigate the enhancement of their acetone sensing properties | |
| Shah et al. | Room-temperature chemiresistive gas sensing of SnO2 nanowires: a review | |
| Zhu et al. | High-performance ethanol sensor based on In2O3 nanospheres grown on silicon nanoporous pillar array | |
| Sun et al. | Au-loaded Zn2SnO4/SnO2/ZnO nanosheets for fast response and highly sensitive TEA gas sensors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190423 |
|
| RJ01 | Rejection of invention patent application after publication |