CN108299641A - A kind of preparation method of polyaniline/ferric oxide composite material - Google Patents
A kind of preparation method of polyaniline/ferric oxide composite material Download PDFInfo
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- CN108299641A CN108299641A CN201810143007.7A CN201810143007A CN108299641A CN 108299641 A CN108299641 A CN 108299641A CN 201810143007 A CN201810143007 A CN 201810143007A CN 108299641 A CN108299641 A CN 108299641A
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- composite material
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- polyaniline
- ferric oxide
- oxide composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
Abstract
A kind of preparation method of polyaniline/ferric oxide composite material, it is related to a kind of gas sensitive.The present invention is to solve existing PANI/Fe2O3The high degree of dispersion of the synthetic method of composite material iron oxide and polymer complex, difficult to realize, and then the technical issues of influence its air-sensitive performance.Preparation method：By FeCl3The hydrochloric acid solution of solution and aniline mixes, and in stainless steel from pressure reaction kettle, sealing is reacted 2 6h at 60 140 DEG C, centrifuged after cooled to room temperature, obtains blackish green precipitation, washing, be lyophilized to get.The synthetic method of the present invention is simple, and PANI/Fe is prepared using a step hydrothermal synthesis method2O3Composite material, synthesis is required at low cost, and post-processing is simple, and product is easily isolated purification.It is easy to mass produce.The material structure of the present invention is stablized, and pattern is uniform, and has excellent detection performance to ammonia, and minimum detectability 0.3ppm, the sensitivity for 100ppm ammonias is 3.79, and the response time is very fast, is 76.2s.The invention belongs to the preparation fields of gas sensitive.
Description
Technical field
The present invention relates to a kind of gas sensitives.
Background technology
Ammonia is a kind of gas of colourless irritant smell, it has strong impulse effect to skin and eyes, excessive
Sucking ammonia can cause the disease of mankind's expiratory system.Therefore it is significant to develop highly sensitive room temperature ammonia gas sensor.Mesh
Before, metal oxide semiconductor sensor is widely used in ammonia because of the advantages that its stability is good, high sensitivity, fast response time
Detection.Common metal oxide has ZnO, TiO2、SnO2、WO3And Fe2O3Deng.But the work of metal oxide semiconductor sensor
It is usually higher to make temperature, in order to reduce its operating temperature, it will usually be doped or compound be modified to metal oxide.It leads
Electric polymer is applied to as composite material in gas sensor because it is with good electric conductivity, common conductive poly-
Closing object has polyaniline (PANI), polypyrrole (PPy) and polythiophene (PT) etc..
In recent years, conducting polymer has obtained extensive concern.Common conducting polymer has, and polyaniline (PANI) gathers
Pyrroles (PPy), polythiophene (PT) etc..Wherein, since polyaniline synthetic method is simple, the advantages that production cost is low, and plasticity is good
It is widely used.Also, polyaniline is a kind of effective material for realizing room temperature detection ammonia.Common polyaniline and metal oxidation
The compound sensitive material of object has PANI/Fe2O3, PANI/ZnO, PANI/SnO2,PANI/TiO2And PANI/In2O3Deng.Wherein, oxygen
Change iron have many advantages, such as good light resistance, weatherability, and it is cheap and easy to get, environmentally protective get the attention, when its with
Air-sensitive performance is greatly improved after polyaniline is compound.In existing report, PANI/Fe is synthesized2O3Common method be usually
Secondary compound or mechanical mixing etc..Such as：D.K.Bandgar et al. synthesizes polyphenyl by chemical oxidative polymerization method first
Then amine uses the method synthetic iron oxide of collosol and gel, so that the two is mixed and made into sensor by magnetic agitation.Yang Li
Et al. by hydro-thermal process contain FeCl3With the electro spinning nano fiber of PVB, make Fe2O3Nanometer sheet growth in situ is on gold electrode, so
Pass through chemical oxidising polymerisation aniline afterwards.Fe will be grown using automatic dip-coating machine2O3The gold electrode of nanometer sheet is immersed in the water of polyaniline
It is dry in solution, it obtains being based on Fe2O3The gas sensor of/PANI nanocomposites.Wang et al. is with PANI-Mo3O10It receives
Rice noodles are template, remove Mo3O10The PANI of multichannel nanotube is obtained, Fe is grown on the surfaces PANI by hydro-thermal reaction2O3It receives
Rice.It follows that the PANI/Fe reported at present2O3The synthetic method of composite material is complex, is mostly to be respectively synthesized out polyphenyl
Then amine and iron oxide make the two be combined with each other by means such as dip-coating, assembling or mechanical mixtures.Oxygen difficult to realize in this way
Change the high degree of dispersion of iron and polymer, and then influences its air-sensitive performance.
Invention content
The purpose of the present invention is to solve existing PANI/Fe2O3The synthetic method of composite material is complex, is difficult
The technical issues of realizing the high degree of dispersion of iron oxide and polymer, and then influencing its air-sensitive performance, provides a kind of polyaniline/oxygen
Change the preparation method of iron composite material.
A kind of preparation method of polyaniline/ferric oxide composite material follows the steps below：
One, by the FeCl of 0.01-0.04mol3·6H2O is dissolved in 5-15mL deionized waters, magnetic agitation 20-45min；
Two, 0.002-0.006mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 5-15mL, magnetic agitation 20-
45min；
Three, the solution obtained by step 1 and the solution obtained by step 2 are mixed, is transferred to polytetrafluoroethyllining lining
Stainless steel from pressure reaction kettle in, sealing, 2-6h is reacted at 60-140 DEG C, centrifuges, obtains after cooled to room temperature
Blackish green precipitation is lyophilized after being washed 3-5 times respectively with ethyl alcohol and deionized water with freeze dryer, freeze-drying time be 24-36h to get
To PANI/Fe2O3Composite material.
The present invention has the advantages that：
(1) synthetic method of the invention is simple, and PANI/Fe is prepared using a step hydrothermal synthesis method2O3Composite material closes
At required at low cost, post-processing is simple, and product is easily isolated purification.It is easy to mass produce.The synthetic method system is used at present
Standby PANI/Fe2O3Composite material is there is not yet document report.
(2) material structure of the invention is stablized, and pattern is uniform, and has excellent detection performance, minimum detection to ammonia
It is limited to 0.3ppm, the sensitivity for 100ppm ammonias is 3.79, and the response time is very fast, is 76.2s.
Description of the drawings
Fig. 1 is to test a PANI/Fe prepared2O3The scanning electron microscope (SEM) photograph of composite material；
Fig. 2 is to test a PANI/Fe prepared2O3The transmission electron microscope picture of composite material；
Fig. 3 is to test a PANI/Fe prepared2O3The XRD diagram of composite material；
Fig. 4 is to test a PANI/Fe prepared2O3Composite material is at room temperature to concentration-sensitivity of various concentration ammonia
Curve；
Fig. 5 is to test a PANI/Fe prepared2O3Composite material is at room temperature to concentration-sensitivity of various concentration ammonia
Curve；
Fig. 6 is to test a PANI/Fe prepared2O3Composite material is at room temperature to the response-recovery of various concentration ammonia song
Line；
Fig. 7 is to test a PANI/Fe prepared2O3Composite material is at room temperature to the response-recovery of various concentration ammonia song
Line.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：In present embodiment a kind of preparation method of polyaniline/ferric oxide composite material according to
Lower step carries out：
One, by the FeCl of 0.01-0.04mol3·6H2O is dissolved in 5-15mL deionized waters, magnetic agitation 20-45min；
Two, 0.002-0.006mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 5-15mL, magnetic agitation 20-
45min；
Three, the solution obtained by step 1 and the solution obtained by step 2 are mixed, is transferred to polytetrafluoroethyllining lining
Stainless steel from pressure reaction kettle in, sealing, 2-6h is reacted at 60-140 DEG C, centrifuges, obtains after cooled to room temperature
Blackish green precipitation is lyophilized after being washed 3-5 times respectively with ethyl alcohol and deionized water with freeze dryer, freeze-drying time be 24-36h to get
To PANI/Fe2O3Composite material.
Specific implementation mode two：The present embodiment is different from the first embodiment in that by 0.02mol's in step 1
FeCl3·6H2O is dissolved in 8mL deionized waters, magnetic agitation 25min.It is other same as the specific embodiment one.
Specific implementation mode three：It will in step 1 unlike one of present embodiment and specific implementation mode one or two
The FeCl of 0.03mol3·6H2O is dissolved in 10mL deionized waters, magnetic agitation 30min.It is other with specific implementation mode one or
One of two is identical.
Specific implementation mode four：It will in step 2 unlike one of present embodiment and specific implementation mode one to three
0.003mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 6mL, magnetic agitation 22min.Other and specific implementation mode one
It is identical to one of three.
Specific implementation mode five：It will in step 2 unlike one of present embodiment and specific implementation mode one to four
0.004mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 8mL, magnetic agitation 25min.Other and specific implementation mode one
It is identical to one of four.
Specific implementation mode six：It will in step 2 unlike one of present embodiment and specific implementation mode one to five
0.005mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 12mL, magnetic agitation 30min.Other and specific implementation mode one
It is identical to one of five.
Specific implementation mode seven：In step 3 unlike one of present embodiment and specific implementation mode one to six
3h is reacted at 70-130 DEG C.It is other identical as one of specific implementation mode one to six.
Specific implementation mode eight：In step 3 unlike one of present embodiment and specific implementation mode one to seven
2-6h is reacted at 80-120 DEG C.It is other identical as one of specific implementation mode one to seven.
Specific implementation mode nine：In step 3 unlike one of present embodiment and specific implementation mode one to eight
4h is reacted at 110 DEG C.It is other identical as one of specific implementation mode one to eight.
Specific implementation mode ten：It is lyophilized in step 3 unlike one of present embodiment and specific implementation mode one to nine
Time is 30h.It is other identical as one of specific implementation mode one to nine.
Using following experimental verifications effect of the present invention：
Experiment one：
A kind of preparation method of polyaniline/ferric oxide composite material follows the steps below：
One, by the FeCl of 0.015mol3·6H2O is dissolved in 10mL deionized waters, magnetic agitation 30min；
Two, 0.005mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 10mL, magnetic agitation 30min；
Three, the solution obtained by step 1 and the solution obtained by step 2 are mixed, being transferred to 50mL has polytetrafluoroethylene (PTFE)
The stainless steel of liner from pressure reaction kettle, 2h is reacted at 100 DEG C, is centrifuged after cooled to room temperature, obtains ink by sealing
Green precipitate is lyophilized after washing 3 times respectively with ethyl alcohol and deionized water with freeze dryer, and freeze-drying time is for 24 hours to get to PANI/
Fe2O3Composite material.
It is prepared by gas sensor：
By PANI/Fe2O3Composite material is coated after being mixed by the mass ratio of 1 ︰ 3 with ethyl alcohol to the aluminium oxide for being coated with gold electrode
Ceramic pipe surface is dried 2-4h in 50-80 DEG C, a heater strip is put into ceramic tube, and its integral solder is obtained on pedestal
To PANI/Fe2O3Composite material device.
Air-sensitive performance is tested：Using static volumetric method, its sensitive property to ammonia, the meter of sensitivity are tested at room temperature
At last:S=Rg/Ra, Rg and Ra are the resistance when reaching stable in testing gas and air respectively.
PANI/Fe2O3Composite material is that nanofiber uniform by pattern, that diameter is about 50nm is accumulated, Fe2O3It receives
Rice corpuscles is dispersed in polyaniline surface.The content of iron oxide.The material sensors show ammonia gas in room temperature
Excellent air-sensitive performance.
By Fig. 4, Fig. 5 it is found that at room temperature as ammonia concentration improves, manufactured PANI/Fe2O3Composite material device
Sensitivity gradually increases, and lowest detection is limited to 0.3ppm, and has preferable linear relationship in detection range.By Fig. 6, Fig. 7
Understand PANI/Fe2O3Composite material device has a response characteristic faster to 100ppm ammonias, response time 76.2s,
Recovery time in 524s, shows the PANI/Fe within the scope of concentration 0.3ppm~100ppm2O3Composite material can be used for measuring ammonia
Gas.
Claims (10)
1. a kind of preparation method of polyaniline/ferric oxide composite material, it is characterised in that a kind of polyaniline/ferric oxide composite material
Preparation method follow the steps below：
One, by the FeCl of 0.01-0.04mol3·6H2O is dissolved in 5-15mL deionized waters, magnetic agitation 20-45min；
Two, 0.002-0.006mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 5-15mL, magnetic agitation 20-45min；
Three, the solution obtained by step 1 and the solution obtained by step 2 are mixed, is transferred to polytetrafluoroethyllining lining not
Steel become rusty from pressure reaction kettle, sealing is reacted 2-6h at 60-140 DEG C, centrifuged after cooled to room temperature, obtained blackish green
Color precipitate, be lyophilized with freeze dryer after being washed 3-5 time respectively with ethyl alcohol and deionized water, freeze-drying time for 24-36h to get to
PANI/Fe2O3Composite material.
2. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 1
By the FeCl of 0.02mol3·6H2O is dissolved in 8mL deionized waters, magnetic agitation 25min.
3. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 1
By the FeCl of 0.03mol3·6H2O is dissolved in 10mL deionized waters, magnetic agitation 30min.
4. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 2
0.003mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 6mL, magnetic agitation 22min.
5. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 2
0.004mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 8mL, magnetic agitation 25min.
6. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 2
0.005mol aniline is dissolved in the hydrochloric acid of a concentration of 1mol/L of 12mL, magnetic agitation 30min.
7. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 3
3h is reacted at 70-130 DEG C.
8. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 3
2-6h is reacted at 80-120 DEG C.
9. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that in step 3
4h is reacted at 110 DEG C.
10. a kind of preparation method of polyaniline/ferric oxide composite material according to claim 1, it is characterised in that step 3
Middle freeze-drying time is 30h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225325A (en) * | 2018-09-11 | 2019-01-18 | 西安交通大学 | Fe-PANI/ zeolite catalyst and preparation method thereof |
| CN111974460A (en) * | 2020-07-06 | 2020-11-24 | 济南大学 | Preparation method of nano Fe-based compound loaded conductive polymer |
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| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN105924963A (en) * | 2016-06-06 | 2016-09-07 | 上海应用技术学院 | Preparation method of graphene/ ferric oxide/ polyaniline composite material |
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2018
- 2018-02-11 CN CN201810143007.7A patent/CN108299641B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN105924963A (en) * | 2016-06-06 | 2016-09-07 | 上海应用技术学院 | Preparation method of graphene/ ferric oxide/ polyaniline composite material |
Non-Patent Citations (3)
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|---|
| ZHIMING ZHANG ET AL.: "Chemical One Step Method to Prepare Polyaniline Nanofibers with Electromagnetic Function", 《MACROMOLECULAR RAPID COMMUNICATIONS》 * |
| 刘红缨 等: "水热法制备聚苯胺及其铁氧化物纳米复合材料", 《高等学校化学学报》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225325A (en) * | 2018-09-11 | 2019-01-18 | 西安交通大学 | Fe-PANI/ zeolite catalyst and preparation method thereof |
| CN109225325B (en) * | 2018-09-11 | 2020-07-28 | 西安交通大学 | Fe-PANI/zeolite catalyst and preparation method thereof |
| CN111974460A (en) * | 2020-07-06 | 2020-11-24 | 济南大学 | Preparation method of nano Fe-based compound loaded conductive polymer |
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