CN106770492A - A kind of composite nano fiber gas sensitive of Graphene doped stannum oxide modification and preparation method thereof - Google Patents
A kind of composite nano fiber gas sensitive of Graphene doped stannum oxide modification and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of composite nano fiber gas sensitive of Graphene doped stannum oxide modification, is composed of the following raw materials by weight：Pyrrole monomer 35 50, polyvinyl alcohol 15 24, zinc nitrate 13 25, N, N dimethylformamide 40 55, p-methyl benzenesulfonic acid 5 10, ferric trichloride 70 95, copper nitrate 5 11, appropriate deionized water, appropriate absolute ethyl alcohol, butter of tin 38, graphite oxide 0.4 1, ammoniacal liquor 20 35, hydrazine hydrate 25.The present invention generates polyvinyl alcohol/zinc salt composite nano fiber using method of electrostatic spinning in substrate, again zinc oxide nano fiber material is obtained through calcining, situ aggregation method is used afterwards, it is obtained with zinc oxide fiber as sandwich layer, sandwich with polypyrrole as cortex, then the composite nano-fiber material of Supported CuO is obtained using infiltration, calcining, the specific surface area increase of material can the extensive use in terms of toxic and harmful detection with monitoring.
Description
Technical field
The present invention relates to gas sensing property Material Field, and in particular to a kind of composite Nano of Graphene doped stannum oxide modification is fine
Dimension gas sensitive and preparation method thereof.
Background technology
The discharge of production waste gas, vehicle exhaust etc. reduces air quality, caused by inflammable gas in fire explosion, coal gas
In rapid succession, detection and monitoring to toxic and harmful become particularly important to malicious accident.But the nanometer air-sensitive material of single structure
Material often exist material in itself easily " reunions ", specific surface is low, air-sensitive performance is unstable, sensitivity is relatively low, test temperature is higher, select
The shortcomings of selecting property difference, improves its specific surface to improve air-sensitive performance, it is necessary to construct multilevel hierarchy nano composite material.
Electrostatic spinning as preparing 1-dimention nano fiber common method, with process controllability, repeatability, operable
Property, fibre dimensions controllability the advantages of, the 3 D stereo nano fibrous membrane prepared by the technology have specific surface area higher,
The advantages of abundant pore structure, controllable packed structures, be conducive to the diffusion and absorption in gas tunica fibrosa, be that one kind prepares height
The preferable nano material of performance sensing element.
Zhang Yue, Qin little Hong et al. are at it《Application and research of the Static Spinning oriented nanofibers yarn in gas sensor》
In one text, the polyacrylonitrile of orientation is continuously prepared using improved electrostatic spinning apparatus（PAN）Nano-fibre yams, then by original
The method of position polymerization synthesizes polypyrrole on the surface of PAN nano-fibre yams respectively（PPy）Or polyaniline（PANI）, formation takes
To and PAN/PPy the and PAN/PANI Coaxial Nanofibers yarns that are evenly coated.It is fixed in and gas is made in interdigital electrode
Quick element, has excellent sensitivity to ammonia, dichloromethane, ethanol and acetone, and there is good air-sensitive to select to ammonia for it
Selecting property.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of composite nano fiber gas of Graphene doped stannum oxide modification
Quick material and preparation method thereof, improves sensing element to NH3、H2The sensitivity of various toxic and harmfuls such as S, NO, and have
Stability higher.
A kind of composite nano fiber gas sensitive of Graphene doped stannum oxide modification, by the raw material group of following weight portion
Into：Pyrrole monomer 35-50 parts, polyvinyl alcohol 15-24 parts, zinc nitrate 13-25 parts, DMF 40-55 parts, to first
Benzene sulfonic acid 5-10 parts, ferric trichloride 70-95 parts, copper nitrate 5-11 parts, appropriate deionized water, appropriate absolute ethyl alcohol, butter of tin
3-8 parts, graphite oxide 0.4-1 parts, ammoniacal liquor 20-35 parts, hydrazine hydrate 2-5 parts.
Step is as follows：
（1）Polyvinyl alcohol/zinc salt composite nano fiber：
Polyvinyl alcohol is added in DMF solvent, after after its dissolving, to zinc nitrate is added in liquid, by it
It is placed in constant temperature blender with magnetic force and is well mixed, solution is placed in and persistently stir at room temperature 20-24 hours to solution clear,
Polyvinyl alcohol/zinc salt precursor solution is obtained, precursor solution is then carried out into injection electrostatic spinning, obtain polyvinyl alcohol/zinc
Salt composite nano fiber；
（2）The preparation of zinc oxide nano fiber：
By step（1）The composite nano fiber of gained is calcined in being placed on Muffle furnace, according to the heating rate of 2-10 DEG C/min
500-600 DEG C is warming up to, calcining at constant temperature 3-6 hours, room temperature is then cooled to, zinc oxide nano fiber is obtained；
（3）The preparation of polypyrrole/zinc oxide compound nano fiber：
1., at room temperature, by p-methyl benzenesulfonic acid dissolving in deionized water, the p-methyl benzenesulfonic acid solution of 4mmol/L is configured to, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 30-50 minutes, is set to solution A；Ferric trichloride is dissolved in deionization again
In the aqueous solution, after stirring, solution B is set to；
2., B solution is added dropwise in solution A, solution is sufficiently stirred for 20-40 minutes, afterwards by step（2）Zinc oxide nano
Rice fiber impregnation is placed under 0 DEG C of environment in the mixed solution, and reaction took out nanofiber after 3-5 hours, used deionization
Water and absolute ethyl alcohol are cleaned repeatedly, are dried in air dry oven 1-3 hours, obtain polypyrrole/zinc oxide compound nano fiber；
（4）The composite nano-fiber material of Supported CuO：
By step（3）Gained composite nano fiber and copper nitrate are added in ethanol simultaneously, solution ultrasonic disperse 40-60 minutes,
2-3 hour is stood afterwards, gained is deposited in 50-70 DEG C of drying, calcined 7-9 hours at 500-600 DEG C in the Muffle furnace afterwards, oneself
So it is cooled to the composite nano-fiber material that room temperature obtains final product Supported CuO；
（5）The preparation of gas sensitive：
1., by wiring solution-forming in butter of tin addition ethanol, by graphite oxide addition deionized water, ultrasonic disperse 40-70 divides
Clock, is subsequently adding the ethanol solution of above-mentioned butter of tin and antimony chloride, ammoniacal liquor and hydrazine hydrate is added after being well mixed, in 55-65
DEG C reaction 2-3 hour, be warming up to 95-100 DEG C continue react 3-5 hours, cool down centrifugation be precipitated thing, be washed with deionized
After drying, Graphene doped stannum oxide is obtained standby；
2., by step（4）The composite nano-fiber material of Supported CuO is with ethanol with 4:1 ratio is added in agate mortar, edge
Same direction uniformly to grind, be tuned into pasty state, add said mixture to continue to grind 30-60 minutes, at 600-800 DEG C
Sintering 2-4 hours, obtains the composite nano fiber gas sensitive of Graphene doped stannum oxide modification.
Wherein, described step（1）Injection electrostatic spinning comprise the following steps that：Precursor solution is added to electrostatic
In the injection needle of device for spinning, syringe needle is connect into high-voltage power supply, then receiving terminal ground connection be 10kV-20kV in voltage, receive away from
Under the conditions of for 8cm-20cm, with micro pump with driving velocity 0.1ml/hr-1ml/hr, substrate is expelled to by injection apparatus
On carry out electrostatic spinning.
Compared with prior art, the invention has the advantages that：
（1）The present invention generates polyvinyl alcohol/zinc salt composite nano fiber using method of electrostatic spinning in substrate, then is obtained through calcining
The netted and fibrous zinc oxide nano fiber material for coexisting, increases the surface area in zinc oxide nano fiber unit volume, it
Situ aggregation method is used afterwards, the surface that polypyrrole is evenly coated at zinc oxide nano fiber is prepared, and is formd with zinc oxide fiber
It is sandwich layer, the sandwich with polypyrrole as cortex so that the specific surface area of composite is significantly increased, and is given full play to
The advantage of polypyrrole, zinc oxide, improves composite to NH3、H2The sensitivity of various toxic and harmfuls such as S, NO.
（2）The present invention obtains the composite nano-fiber material of Supported CuO using infiltration, calcining afterwards, increases compound fibre
Dimension material and the specific surface area of gas effect, and increased the avtive spot of material surface so that the sensitivity of material for gaseous
Increase, in addition when the material is exposed to containing H2When in S gaseous environments, can be reacted in material surface, the CuO of semiconductor property
Be transformed into the conductor CuS of metallicity so that the material resistance is greatly lowered, thus Supported CuO composite nano-fiber material
To H2S has selectivity and high sensitivity well.
（3）The present invention using Graphene doped stannum oxide have specific surface area greatly, particle size uniformity and in nanometer range,
Its sensitivity and selectivity to gas response is improve, so that the gas sensor for preparing has excellent gas-sensitive property,
Suitable for atmosphere environment supervision and mine gas leakage monitoring.
Specific embodiment
A kind of composite nano fiber gas sensitive of Graphene doped stannum oxide modification, by the raw material group of following weight portion
Into：45 parts of pyrrole monomer, 22 parts of polyvinyl alcohol, 19 parts of zinc nitrate, 55 parts of DMF, 6 parts of p-methyl benzenesulfonic acid, three
90 parts of iron chloride, 9 parts of copper nitrate, appropriate deionized water, appropriate absolute ethyl alcohol, 7 parts of butter of tin, 0.8 part of graphite oxide, ammoniacal liquor
32 parts, 4 parts of hydrazine hydrate.
Step is as follows：
（1）Polyvinyl alcohol/zinc salt composite nano fiber：
Polyvinyl alcohol is added in DMF solvent, after after its dissolving, to zinc nitrate is added in liquid, by it
It is placed in constant temperature blender with magnetic force and is well mixed, solution is placed in and persistently stir at room temperature 22 hours to solution clear, obtains
To polyvinyl alcohol/zinc salt precursor solution, precursor solution is then carried out into injection electrostatic spinning, obtain polyvinyl alcohol/zinc salt
Composite nano fiber；
（2）The preparation of zinc oxide nano fiber：
By step（1）The composite nano fiber of gained is calcined in being placed on Muffle furnace, is heated up according to the heating rate of 5 DEG C/min
To 550 DEG C, then calcining at constant temperature 5 hours is cooled to room temperature, obtains zinc oxide nano fiber；
（3）The preparation of polypyrrole/zinc oxide compound nano fiber：
1., at room temperature, by p-methyl benzenesulfonic acid dissolving in deionized water, the p-methyl benzenesulfonic acid solution of 4mmol/L is configured to, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 40 minutes, is set to solution A；Ferric trichloride is dissolved in deionized water again
In solution, after stirring, solution B is set to；
2., B solution is added dropwise in solution A, solution is sufficiently stirred for 35 minutes, afterwards by step（2）Zinc-oxide nano
Fiber impregnation is placed under 0 DEG C of environment in the mixed solution, and reaction took out nanofiber after 4 hours, with deionized water and
Absolute ethyl alcohol is cleaned repeatedly, is dried 2 hours in air dry oven, obtains polypyrrole/zinc oxide compound nano fiber；
（4）The composite nano-fiber material of Supported CuO：
By step（3）Gained composite nano fiber and copper nitrate are added in ethanol simultaneously, solution ultrasonic disperse 50 minutes, afterwards
2 hours are stood, gained is deposited in 60 DEG C of dryings, calcined 8 hours at 520 DEG C in the Muffle furnace afterwards, naturally cool to room temperature i.e.
Obtain the composite nano-fiber material of Supported CuO；
（5）The preparation of gas sensitive：
1., by butter of tin add ethanol in wiring solution-forming, by graphite oxide add deionized water in, ultrasonic disperse 60 minutes,
The ethanol solution of above-mentioned butter of tin and antimony chloride is subsequently adding, ammoniacal liquor and hydrazine hydrate are added after being well mixed, 3 are reacted at 60 DEG C
Hour, it is warming up to 96 DEG C and continues to react 4 hours, cooling centrifugation is precipitated thing, is washed with deionized after drying, and obtains graphite
Alkene doped stannum oxide is standby；
2., by step（4）The composite nano-fiber material of Supported CuO is with ethanol with 4:1 ratio is added in agate mortar, edge
Same direction uniformly to grind, be tuned into pasty state, sintering 3 is small at adding said mixture to continue to grind 50 minutes, then 780 DEG C
When, obtain the composite nano fiber gas sensitive of Graphene doped stannum oxide modification.
Wherein, described step（1）Injection electrostatic spinning comprise the following steps that：Precursor solution is added to electrostatic
In the injection needle of device for spinning, syringe needle is connect into high-voltage power supply, then receiving terminal ground connection be 15kV in voltage, and receiving distance is
Under the conditions of 10cm, with micro pump with driving velocity 0.5ml/hr, being expelled to by injection apparatus carries out electrostatic spinning in substrate.
Gas sensing property test is carried out under the conditions of 100 DEG C：
Sensitivity to 10ppm hydrogen sulfide gas is 421, response time：≤ 1min, recovery time：≤2min.
Claims (3)
1. the composite nano fiber gas sensitive that a kind of Graphene doped stannum oxide is modified, it is characterised in that by following weight portion
Raw material composition：Pyrrole monomer 35-50 parts, polyvinyl alcohol 15-24 parts, zinc nitrate 13-25 parts, DMF 40-
55 parts, p-methyl benzenesulfonic acid 5-10 parts, ferric trichloride 70-95 parts, copper nitrate 5-11 parts, appropriate deionized water, appropriate absolute ethyl alcohol,
Butter of tin 3-8 parts, graphite oxide 0.4-1 parts, ammoniacal liquor 20-35 parts, hydrazine hydrate 2-5 parts.
2. according to claims 1 a kind of Graphene doped stannum oxide modification composite nano fiber gas sensitive system
Preparation Method, it is characterised in that step is as follows：
（1）Polyvinyl alcohol/zinc salt composite nano fiber：
Polyvinyl alcohol is added in DMF solvent, after after its dissolving, to zinc nitrate is added in liquid, by it
It is placed in constant temperature blender with magnetic force and is well mixed, solution is placed in and persistently stir at room temperature 20-24 hours to solution clear,
Polyvinyl alcohol/zinc salt precursor solution is obtained, precursor solution is then carried out into injection electrostatic spinning, obtain polyvinyl alcohol/zinc
Salt composite nano fiber；
（2）The preparation of zinc oxide nano fiber：
By step（1）The composite nano fiber of gained is calcined in being placed on Muffle furnace, according to the heating rate of 2-10 DEG C/min
500-600 DEG C is warming up to, calcining at constant temperature 3-6 hours, room temperature is then cooled to, zinc oxide nano fiber is obtained；
（3）The preparation of polypyrrole/zinc oxide compound nano fiber：
1., at room temperature, by p-methyl benzenesulfonic acid dissolving in deionized water, the p-methyl benzenesulfonic acid solution of 4mmol/L is configured to, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 30-50 minutes, is set to solution A；Ferric trichloride is dissolved in deionization again
In the aqueous solution, after stirring, solution B is set to；
2., B solution is added dropwise in solution A, solution is sufficiently stirred for 20-40 minutes, afterwards by step（2）Zinc oxide nano
Rice fiber impregnation is placed under 0 DEG C of environment in the mixed solution, and reaction took out nanofiber after 3-5 hours, used deionization
Water and absolute ethyl alcohol are cleaned repeatedly, are dried in air dry oven 1-3 hours, obtain polypyrrole/zinc oxide compound nano fiber；
（4）The composite nano-fiber material of Supported CuO：
By step（3）Gained composite nano fiber and copper nitrate are added in ethanol simultaneously, solution ultrasonic disperse 40-60 minutes,
2-3 hour is stood afterwards, gained is deposited in 50-70 DEG C of drying, calcined 7-9 hours at 500-600 DEG C in the Muffle furnace afterwards, oneself
So it is cooled to the composite nano-fiber material that room temperature obtains final product Supported CuO；
（5）The preparation of gas sensitive：
1., by wiring solution-forming in butter of tin addition ethanol, by graphite oxide addition deionized water, ultrasonic disperse 40-70 divides
Clock, is subsequently adding the ethanol solution of above-mentioned butter of tin and antimony chloride, ammoniacal liquor and hydrazine hydrate is added after being well mixed, in 55-65
DEG C reaction 2-3 hour, be warming up to 95-100 DEG C continue react 3-5 hours, cool down centrifugation be precipitated thing, be washed with deionized
After drying, Graphene doped stannum oxide is obtained standby；
2., by step（4）The composite nano-fiber material of Supported CuO is with ethanol with 4:1 ratio is added in agate mortar, edge
Same direction uniformly to grind, be tuned into pasty state, add said mixture to continue to grind 30-60 minutes, at 600-800 DEG C
Sintering 2-4 hours, obtains the composite nano fiber gas sensitive of Graphene doped stannum oxide modification.
3. according to claims 2 a kind of Graphene doped stannum oxide modification composite nano fiber gas sensitive system
Preparation Method, it is characterised in that described step（1）Injection electrostatic spinning comprise the following steps that：Precursor solution is added
To in the injection needle of electrostatic spinning apparatus, syringe needle is connect into high-voltage power supply, then receiving terminal ground connection be 10kV-20kV in voltage,
Distance is received under the conditions of 8cm-20cm, with micro pump with driving velocity 0.1ml/hr-1ml/hr, to be noted by injection apparatus
Being mapped to carries out electrostatic spinning in substrate.
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| CN115247002A (en) * | 2022-08-08 | 2022-10-28 | 安徽锦华氧化锌有限公司 | Preparation method of static conductive zinc oxide |
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| CN101182680A (en) * | 2007-10-29 | 2008-05-21 | 东北林业大学 | Cellulose fabrics/olypyrrole electrostatic resistance compound material and method of producing the same |
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Application publication date: 20170531 |