CN106501324A - A kind of composite nano fiber gas sensitive of load cadmium sulfide cladding CuO and preparation method thereof - Google Patents
A kind of composite nano fiber gas sensitive of load cadmium sulfide cladding CuO and preparation method thereof Download PDFInfo
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- CN106501324A CN106501324A CN201610988708.1A CN201610988708A CN106501324A CN 106501324 A CN106501324 A CN 106501324A CN 201610988708 A CN201610988708 A CN 201610988708A CN 106501324 A CN106501324 A CN 106501324A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The present invention discloses the composite nano fiber gas sensitive that a kind of load cadmium sulfide coats CuO, is made up of the raw material of following weight portion：Pyrrole monomer 35 50, polyvinyl alcohol 16 27, zinc nitrate 15 24, N, N dimethylformamide 45 65, p-methyl benzenesulfonic acid 6 12, ferric chloride 90 115, copper nitrate 5 11, appropriate deionized water, appropriate dehydrated alcohol, thioacetamide 24, cadmium acetate 6 12, nano-sized iron oxide 25.The present invention generates polyvinyl alcohol/zinc salt composite nano fiber in substrate using method of electrostatic spinning, zinc oxide nano fiber material is obtained again through calcining, situ aggregation method is adopted afterwards, it has been 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 of material is significantly increased, can extensively apply at toxic and harmful detection and the aspects such as monitoring.
Description
Technical field
The present invention relates to gas sensing property Material Field, and in particular to a kind of load cadmium sulfide coats the composite nano fiber of CuO
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
Malicious accident in rapid succession, becomes particularly important to the detection and monitoring of toxic and harmful.But the nanometer air-sensitive material of single structure
Often there is material itself easy " reunion " in material, specific surface is low, air-sensitive performance is unstable, sensitivity is relatively low, test temperature is higher, choosing
The shortcomings of selecting property difference, need to construct multilevel hierarchy nano composite material and improve its specific surface to improve air-sensitive performance.
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 higher specific surface area,
The advantages of abundant pore structure, controllable packed structures, be conducive to the diffusion and absorption in gas fibrous membrane, be that one kind prepares height
The preferable nano material of performance sensing element.
Zhang Yue, Qin little Hong et al. are at which《Application and research of the Static Spinning oriented nanofibers yarn in gas sensor》
In one text, the polyacrylonitrile that continuously prepares orientation using improved electrostatic spinning apparatus（PAN）Nano-fibre yams, then by original
The method of position polymerization is respectively in the surface synthesis polypyrrole of PAN nano-fibre yams（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 interdigital electrode and makes gas
Quick element, has excellent susceptiveness, and which has good air-sensitive choosing to ammonia to ammonia, dichloromethane, ethanol and acetone
Selecting property.
Content of the invention
For the deficiencies in the prior art, the present invention provides the composite nano fiber air-sensitive that a kind of load cadmium sulfide coats CuO
Material and preparation method thereof, improves sensing element to NH3、H2The susceptiveness of multiple toxic and harmfuls such as S, NO, and have compared with
High stability.
A kind of load cadmium sulfide coats the composite nano fiber gas sensitive of CuO, is made up of the raw material of following weight portion：Pyrrole
Cough up monomer 35-50 parts, polyvinyl alcohol 16-27 parts, zinc nitrate 15-24 parts, DMF 45-65 parts, to toluene sulphur
Sour 6-12 parts, ferric chloride 90-115 parts, copper nitrate 5-11 parts, appropriate deionized water, appropriate dehydrated alcohol, thioacetamide 2-
4 parts, cadmium acetate 6-12 parts, nano-sized iron oxide 2-5 parts.
Step is as follows：
（1）Polyvinyl alcohol/zinc salt composite nano fiber：
Polyvinyl alcohol is added in DMF solvent, after which dissolves, zinc nitrate is added in liquid, by which
Mix homogeneously in constant temperature blender with magnetic force is placed on, solution is put and persistently stir at room temperature 20-24 hours to solution clear,
Polyvinyl alcohol/zinc salt precursor solution is obtained, precursor solution is carried out injection electrostatic spinning then, 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 placed in Muffle furnace to be calcined, according to the heating rate of 2-10 DEG C/min
500-600 DEG C is warming up to, then calcining at constant temperature 3-6 hour is cooled to room temperature, obtains zinc oxide nano fiber；
（3）The preparation of polypyrrole/zinc oxide compound nano fiber：
1., at room temperature, p-methyl benzenesulfonic acid is dissolved in deionized water, is configured to the p-methyl benzenesulfonic acid solution of 4mmol/L, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 30-50 minutes, is set to solution A；Ferric chloride is dissolved in deionization again
In 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, takes out nanofiber, use deionization after reaction 3-5 hours
Water and dehydrated alcohol are cleaned repeatedly, dry 1-3 hours in air dry oven, obtain polypyrrole/zinc oxide compound nano fiber；
（4）Load cadmium sulfide coats the composite nano-fiber material of CuO：
By step（3）Gained composite nano fiber and copper nitrate are added simultaneously in ethanol, solution ultrasonic disperse 40-60 minutes,
Stand 2-3 hours afterwards, add thioacetamide and continue supersound process 20-60 minute, add cadmium acetate to continue ultrasound afterwards
30-50 minutes, then be stirred at reflux under 85-100 DEG C of water-bath, cooled and filtered, washing, drying, afterwards 500- in Muffle furnace
7-9 hours are calcined at 600 DEG C, are naturally cooled to room temperature and are obtained final product the composite nano-fiber material that load cadmium sulfide coats CuO；
（5）The preparation of gas sensitive：
By step（4）Composite nano-fiber material and the ethanol of load cadmium sulfide cladding CuO is with 4:1 ratio is added to Achatess and grinds
In alms bowl, uniformly grind along same direction, be tuned into pasty state, add nano-sized iron oxide to continue grinding 30-60 minutes, then at 600-
2-4 hours are sintered at 800 DEG C, obtain the composite nano fiber gas sensitive that a kind of load cadmium sulfide coats CuO.
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 high-voltage power supply, receiving terminal is grounded, is then 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 in substrate using method of electrostatic spinning, then obtains 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
Afterwards using situ aggregation method, the surface that polypyrrole is evenly coated at zinc oxide nano fiber is prepared, is defined with zinc oxide fiber
For 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
Polypyrrole, the advantage of zinc oxide, improve composite to NH3、H2The susceptiveness of multiple 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 react in material surface, the CuO of semiconductor property
It is transformed into metallic conductor CuS so that the material resistance is greatly lowered, therefore the composite nano-fiber material of Supported CuO
To H2S has good selectivity and high sensitivity.
（3）The composite nano fiber gas sensitive of load cadmium sulfide cladding CuO working range width when using in the present invention,
For all there is the organic volatile gas of low, high concentration good susceptiveness, response to recover fast, good stability.
Specific embodiment
A kind of load cadmium sulfide coats the composite nano fiber gas sensitive of CuO, is made up of the raw material of following weight portion：Pyrrole
Cough up 50 parts of monomer, 25 parts of polyvinyl alcohol, 22 parts of zinc nitrate, 60 parts of DMF, 10 parts of p-methyl benzenesulfonic acid, tri-chlorination
110 parts of ferrum, 9 parts of copper nitrate, appropriate deionized water, appropriate dehydrated alcohol, 3 parts of thioacetamide, 10 parts of cadmium acetate are nano oxidized
4 parts of ferrum.
Step is as follows：
（1）Polyvinyl alcohol/zinc salt composite nano fiber：
Polyvinyl alcohol is added in DMF solvent, after which dissolves, zinc nitrate is added in liquid, by which
Mix homogeneously in constant temperature blender with magnetic force is placed on, solution is put and persistently stir at room temperature 22 hours to solution clear, obtain
Polyvinyl alcohol/zinc salt precursor solution is arrived, precursor solution is carried out injection electrostatic spinning then, 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 placed in Muffle furnace to be calcined, and heats 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, p-methyl benzenesulfonic acid is dissolved in deionized water, is configured to the p-methyl benzenesulfonic acid solution of 4mmol/L, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 40 minutes, is set to solution A；Ferric chloride 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, reaction 4 hours after nanofiber is taken out, deionized water and
Dehydrated alcohol is cleaned repeatedly, dries 2 hours, obtain polypyrrole/zinc oxide compound nano fiber in air dry oven；
（4）Load cadmium sulfide coats the composite nano-fiber material of CuO：
By step（3）Gained composite nano fiber and copper nitrate are added simultaneously in ethanol, solution ultrasonic disperse 50 minutes, afterwards
3 hours are stood, thioacetamide is added and is continued supersound process 40 minutes, add cadmium acetate to continue ultrasound 40 minutes afterwards, then
It is stirred at reflux under 95 DEG C of water-baths, cooled and filtered, washing, drying, calcines 8 hours at 550 DEG C in Muffle furnace afterwards, natural
It is cooled to room temperature and obtains final product the composite nano-fiber material that load cadmium sulfide coats CuO；
（5）The preparation of gas sensitive：
By step（4）Composite nano-fiber material and the ethanol of load cadmium sulfide cladding CuO is with 4:1 ratio is added to Achatess and grinds
In alms bowl, uniformly grind along same direction, be tuned into pasty state, add nano-sized iron oxide to continue grinding 50 minutes, at 750 DEG C
Sintering 3 hours, obtains the composite nano fiber gas sensitive that a kind of load cadmium sulfide coats CuO.
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 high-voltage power supply, receiving terminal is grounded, be then 15kV in voltage, receiving distance is
Under the conditions of 10cm, with micro pump with driving velocity 0.5ml/hr, being expelled in substrate by injection apparatus carries out electrostatic spinning.
Gas sensing property test is carried out under the conditions of 100 DEG C：
It is 426 to the sensitivity of 10ppm hydrogen sulfide gas, response time：≤ 50s, recovery time：≤100s.
Claims (3)
1. a kind of load cadmium sulfide coats the composite nano fiber gas sensitive of CuO, it is characterised in that by the original of following weight portion
Material composition：Pyrrole monomer 35-50 parts, polyvinyl alcohol 16-27 parts, zinc nitrate 15-24 parts, DMF 45-65 parts,
P-methyl benzenesulfonic acid 6-12 parts, ferric chloride 90-115 parts, copper nitrate 5-11 parts, appropriate deionized water, appropriate dehydrated alcohol are thio
Acetamide 2-4 parts, cadmium acetate 6-12 parts, nano-sized iron oxide 2-5 parts.
2. the preparation of the composite nano fiber gas sensitive of a kind of load cadmium sulfide cladding CuO according to claims 1
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 which dissolves, zinc nitrate is added in liquid, by which
Mix homogeneously in constant temperature blender with magnetic force is placed on, solution is put and persistently stir at room temperature 20-24 hours to solution clear,
Polyvinyl alcohol/zinc salt precursor solution is obtained, precursor solution is carried out injection electrostatic spinning then, 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 placed in Muffle furnace to be calcined, according to the heating rate of 2-10 DEG C/min
500-600 DEG C is warming up to, then calcining at constant temperature 3-6 hour is cooled to room temperature, obtains zinc oxide nano fiber；
（3）The preparation of polypyrrole/zinc oxide compound nano fiber：
1., at room temperature, p-methyl benzenesulfonic acid is dissolved in deionized water, is configured to the p-methyl benzenesulfonic acid solution of 4mmol/L, it
It is slowly added dropwise pyrrole monomer thereto afterwards, is sufficiently stirred for 30-50 minutes, is set to solution A；Ferric chloride is dissolved in deionization again
In 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, takes out nanofiber, use deionization after reaction 3-5 hours
Water and dehydrated alcohol are cleaned repeatedly, dry 1-3 hours in air dry oven, obtain polypyrrole/zinc oxide compound nano fiber；
（4）Load cadmium sulfide coats the composite nano-fiber material of CuO：
By step（3）Gained composite nano fiber and copper nitrate are added simultaneously in ethanol, solution ultrasonic disperse 40-60 minutes,
Stand 2-3 hours afterwards, add thioacetamide and continue supersound process 20-60 minute, add cadmium acetate to continue ultrasound afterwards
30-50 minutes, then be stirred at reflux under 85-100 DEG C of water-bath, cooled and filtered, washing, drying, afterwards 500- in Muffle furnace
7-9 hours are calcined at 600 DEG C, are naturally cooled to room temperature and are obtained final product the composite nano-fiber material that load cadmium sulfide coats CuO；
（5）The preparation of gas sensitive：
By step（4）Composite nano-fiber material and the ethanol of load cadmium sulfide cladding CuO is with 4:1 ratio is added to Achatess and grinds
In alms bowl, uniformly grind along same direction, be tuned into pasty state, add nano-sized iron oxide to continue grinding 30-60 minutes, then at 600-
2-4 hours are sintered at 800 DEG C, obtain the composite nano fiber gas sensitive that a kind of load cadmium sulfide coats CuO.
3. the preparation of the composite nano fiber gas sensitive of a kind of load cadmium sulfide cladding CuO according to claims 2
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 high-voltage power supply, receiving terminal is grounded, be then 10kV-20kV in voltage, connect
Receive under the conditions of for 8cm-20cm, with micro pump with driving velocity 0.1ml/hr-1ml/hr, injected by injection apparatus
Electrostatic spinning is carried out in substrate.
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| CN108179547A (en) * | 2017-12-19 | 2018-06-19 | 东华大学 | A kind of preparation method of the fluorescent nano-fiber film as heavy metal antimony Visual retrieval device |
| CN110064434A (en) * | 2019-03-21 | 2019-07-30 | 天津工业大学 | The preparation method of intrinsic photocatalysis doughnut |
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Cited By (3)
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| CN108179547A (en) * | 2017-12-19 | 2018-06-19 | 东华大学 | A kind of preparation method of the fluorescent nano-fiber film as heavy metal antimony Visual retrieval device |
| CN110064434A (en) * | 2019-03-21 | 2019-07-30 | 天津工业大学 | The preparation method of intrinsic photocatalysis doughnut |
| CN110064434B (en) * | 2019-03-21 | 2021-11-16 | 天津工业大学 | Preparation method of intrinsic photocatalytic hollow fiber |
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Application publication date: 20170315 |