CN103642040A - Method for preparing polypyrrole-tin dioxide hybrid materials - Google Patents
Method for preparing polypyrrole-tin dioxide hybrid materials Download PDFInfo
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- CN103642040A CN103642040A CN201310485684.4A CN201310485684A CN103642040A CN 103642040 A CN103642040 A CN 103642040A CN 201310485684 A CN201310485684 A CN 201310485684A CN 103642040 A CN103642040 A CN 103642040A
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Abstract
The invention discloses a method for preparing polypyrrole-tin dioxide (PPy-SnO2) hybrid materials. The method comprises the steps: (1) taking 1-20 mg of pyrrole monomers, 80-99 mg of tin dioxide, 3.4-68 mg of ammonium persulfate and 40-60 ml of water, mixing according to a proportion, stirring, and carrying out ultrasonic treatment for 30 min; (2) transferring the mixed material to a reaction kettle, placing the reaction kettle in a drying oven with the temperature of 140 DEG C, carrying out a hydrothermal reaction for 8 h, after the reaction is completed, taking out the reaction kettle, naturally cooling to the room temperature, filtering, respectively washing with deionized water, ethanol and acetone for a plurality of times, finally putting the product in the drying oven with the temperature of 60 DEG C for drying, and thus obtaining the PPy-SnO2 hybrid materials. With utilization of the reaction comprising the hydrothermal method and the polymer in-situ generation method happening simultaneously, a series of PPy-SnO2 hybrid materials with different mass fractions of PPy can be prepared. According to the method, one-step completion of the reaction is facilitated, the product is easy to purify and has good selectivity on ethanol gas.
Description
Technical field
The present invention relates to a kind of method of preparing polypyrrole and tindioxide hybrid material, belong to compound preparing technical field.
Background technology
Polypyrrole and tindioxide (Ju Bi Ka ∕ tindioxide) hybrid material is the semiconductor material that contains p-n heterojunction.Wherein, tindioxide is N-shaped Semiconductor gas sensors material, and current carrier is electronics, at high temperature reducing gas is had to susceptibility, in fields such as oil, chemical industry, colliery, environmental protection, house, national defence, enters practical stage.But high, poor selectivity that the deficiency of its existence is working temperature; Polypyrrole (Ppy) is p-type semiconductor material, and current carrier is hole, can make up the shortcoming that tin dioxide material service temperature is high, but response recovery time is long, simultaneously poor selectivity.Adopt mechanical blending method can make polypyrrole and tindioxide (Ju Bi Ka ∕ tindioxide) hybrid material, first prepare polypyrrole, then with tindioxide in proportion machinery mix and obtain.Vapor sensitivity is tested and is shown, under the same terms, the gas sensing property of polypyrrole and tindioxide hybrid material and stability are all better than single polypyrrole, tin dioxide material.But adopt the product obtaining in this way alcohol gas is not had to susceptibility.
Summary of the invention
The object of this invention is to provide a kind of method of preparing polypyrrole and tindioxide (Ju Bi Ka ∕ tindioxide) hybrid material, the method reactions steps is simple, resulting materials is good to alcohol gas selectivity, and working temperature is low, has solved the defect of existing sensor poor selectivity.
It is such that the present invention solves the technical scheme that its technical problem takes:
The present invention utilizes hydrothermal method to react with polymer in situ method of formation is simultaneous, prepares PPy and the SnO of a series of different PPy massfractions
2hybrid material.Experiment showed, preparation method's change, cause PPy and SnO
2the microtexture of hybrid material changes, thereby gives its new gas sensitization performance, and gas sensing property test shows, the PPy that the method obtains and SnO
2(PPy ∕ SnO
2) hybrid material has good selection, susceptibility to alcohol gas.Can be used for gas sensing device technical field.
Concrete, preparation method of the present invention is as follows:
(1) get 1 ~ 20mg pyrrole monomer, 80 ~ 99mg tindioxide, 3.4 ~ 68mg ammonium persulphate, 40 ~ 60ml water (H
+concentration 1mol ∕ L), be mixed in proportion stirring, ultrasonic 30min;
(2) mixture is proceeded to reactor, and reactor is placed in to 140 ℃ of baking ovens, hydro-thermal reaction 8 hours, react complete, take out reactor, naturally cool to room temperature, by sedimentation and filtration, use respectively deionized water, ethanol, washing with acetone for several times, finally product is dried in 60 ℃ of baking ovens, can obtain polypyrrole and tindioxide (poly-pyrrole is coughed up ∕ tindioxide) hybrid material.
The present invention adopts the sensitive property of heater-type method test material: by PPy and SnO
2hybrid material is made heater-type gas sensor, at 90 ℃, by voltage detection method, carries out air-sensitive test.Pull-up resistor is 4.7M Ω, and ambient moisture is 60%.Sensitivity directly represents with voltage.Select ethanol, H
2, CO, NH
3for test gas.
The beneficial effect that the present invention obtains is as follows: preparation method of the present invention utilizes hydrothermal method to react with polymer in situ method of formation is simultaneous, can prepare PPy and the SnO of a series of different PPy massfractions
2hybrid material.The method is conducive to react that a step completes, product is easy to purifying; Products therefrom is good to alcohol gas selectivity.
Accompanying drawing explanation
Fig. 1 is hybrid material PPy (5%) and SnO
2and PPy (20%) and SnO
2x-ray powder diffraction spectrogram.Simultaneously with pure SnO
2compare with the XRD spectra of PPy.As seen from the figure, the XRD spectra of pure PPy shows a wide and blunt diffraction peak, and this is the feature of typical amorphous polymer.PPy (5%) and SnO
2and PPy (20%) and SnO
2hybrid material and pure SnO
2xRD spectra have identical diffraction peak, generation and whole hydro-thermal reaction of this explanation polymer P Py do not affect original SnO
2crystal formation.Meanwhile, due to SnO in hybrid material
2content high, diffraction peak intensity is large, so the diffraction peak of polypyrrole is not obvious.
Fig. 2 is PPy (5%) and SnO
2the scanning electron microscope of hybrid material (a) and transmission electron microscope (b) photo.
From SEM, see the SnO of crystalline state
2nanoparticle and amorphous PPy are dispersed, and PPy is attached to SnO
2surface.TEM picture shows, SnO
2particle diameter all below 20nm, from figure, see most of SnO
2particle edges is clearly demarcated, and lattice line is clear, minority SnO
2because having PPy particle edges, surface thickens.
Fig. 3 is PPy (20%) and SnO
2the x-ray photoelectron spectroscopy figure of hybrid material.
In Fig. 3, provided pure SnO simultaneously
2x-ray photoelectron spectroscopy figure to compare.From figure, see PPy (20%) and SnO
2hybrid material compares SnO
2in many N1s peaks, this can illustrate, SnO
2the existence of surface organic composition PPy; From table 1, the atomic percentage conc of bi-material can be seen simultaneously, PPy (20%) and SnO
2the percentage composition of the C atom on hybrid material surface is far above SnO
2the content on surface; In addition, hybrid material surface also has some O and Sn to exist, and its percentage composition is starkly lower than SnO
2in content, this illustrates SnO
2particle surface is wrapped with skim polypyrrole, or, SnO
2particle is not wrapped up completely by polypyrrole, the SnO that some is exposed
2particle exists.
Fig. 4 is preparation and testing process block diagram.
The gas sensor of preparing in experiment is thick-film type element, and the structure of gas sensor is heater-type structure, adopts static distribution method to measure during test gas.
Fig. 5 is alcohol gas test circuit figure.
In Fig. 5, V
cloop voltage, i.e. test voltage, in test, choosing test voltage is 5V; V
hheater voltage, by regulating different heater voltage values can provide gas sensor required working temperature; R
lbeing the pull-up resistor of connecting with gas sensor, is interchangeable card insert type, according to experiment, needs to choose different resistances; V
outpull-up resistor R
lon voltage.
Fig. 6 (a), (b), (c) are respectively hybrid material PPy (5%) and SnO
2, PPy (10%) and SnO
2and PPy (20%) and SnO
2response recovery curve to alcohol gas at 90 ℃.
From Fig. 6, can see the PPy of different PPy massfractions and SnO
2the good reversibility of hybrid material to the response of alcohol gas, shows the semi-conductive feature of N-shaped.And standby PPy and the SnO of mechanical blending legal system
2hybrid material, under same test condition, does not have susceptibility to alcohol gas.
Table 1
| ? | C1s (%) | O1s (%) | Sn3d (%) | N1s (%) |
| SnO 2 | 49.5 | 35.7 | 14.5 | 0 |
| PPy (20%) and SnO 2 | 70.1 | 20.9 | 5.3 | 3.7 |
Embodiment
The present invention will be further described for following examples, but protection scope of the present invention is not limited to this.
1 one kinds of PPy of embodiment (5%) and SnO
2hybrid material preparation method
Get 50ml distilled water, with HCl, regulate its H
+concentration be about 1mol ∕ L, add 5mg pyrroles, by the ultrasonic dispersion of solution 30min.Add again 95mg SnO
2.By after mixture stirring, ultrasonic each 30min, proceed to reactor, then add 17mg oxygenant ammonium persulphate.Reactor is placed in to 140 ℃ of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, uses respectively deionized water, ethanol, washing with acetone for several times, finally product is dried in 60 ℃ of baking ovens.Obtain PPy (5%) and SnO
2hybrid material.Be made into heater-type gas sensor, at 90 ℃, by voltage detection method, carry out air-sensitive test.Response recovery curve is shown in Fig. 6 (a).
2 one kinds of PPy of embodiment (10%) and SnO
2hybrid material preparation method
Get 50ml distilled water, with HCl, regulate its H
+concentration be about 1mol ∕ L, add 10 mg pyrroles, by the ultrasonic dispersion of solution 30min.Add again 90 mg SnO
2.By after mixture stirring, ultrasonic each 30 min, proceed to reactor, then add 34 mg oxygenant ammonium persulphates.Reactor is placed in to 140 ℃ of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, uses respectively deionized water, ethanol, washing with acetone for several times, finally product is dried in 60 ℃ of baking ovens.Obtain PPy (10%) and SnO
2hybrid material.Be made into heater-type gas sensor, at 90 ℃, by voltage detection method, carry out air-sensitive test.Response recovery curve is shown in Fig. 6 (b).
3 one kinds of PPy of embodiment (20%) and SnO
2hybrid material preparation method
Comparative example 1: mechanical blending legal system is for PPy (20%) and SnO
2hybrid material (reference literature < < Chinese Journal of Inorganic Chemistry > >, 2005,21(7): 977).Technical scheme is as follows: in being furnished with the round-bottomed flask of prolong, add 50ml anhydrous diethyl ether, add a certain amount of anhydrous FeCl under stirring
3, logical N
2gas 20 ~ 30 min, then inject Py with syringe, at N
2in atmosphere, react 1.5 h.Filter, product washs to neutral with distilled water, anhydrous methanol successively, and under room temperature, vacuum-drying 24 h, obtain polypyrrole.With analytical balance, accurately take mass ratio PPy: SnO
2=20:80, is placed in agate mortar, fully grinds, and mechanical blending legal system is for PPy (20%) and SnO
2hybrid material.Be made into heater-type gas sensor, at 90 ℃, by voltage detection method, carry out air-sensitive test.Gas sensing property experiment shows, PPy (20%) and SnO that mechanical blending legal system is standby
2hybrid material does not have susceptibility to alcohol gas.
Comparative example 2: get 50ml distilled water, regulate its H with HCl
+concentration be about 1mol ∕ L, add 20 mg pyrroles, by the ultrasonic dispersion of solution 30min.Add again 80 mg SnO
2.By after mixture stirring, ultrasonic each 30 min, proceed to reactor, then add 68 mg oxygenant ammonium persulphates.Reactor is placed in to 140 ℃ of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, uses respectively deionized water, ethanol, washing with acetone for several times, finally product is dried in 60 ℃ of baking ovens.Obtain PPy (20%) and SnO
2hybrid material.Be made into heater-type gas sensor, at 90 ℃, by voltage detection method, carry out air-sensitive test.Gas sensing property experiment shows, PPy (20%) and SnO prepared by hydrothermal method and polymer in situ method of formation
2hybrid material has good susceptibility to alcohol gas.Response recovery curve is shown in Fig. 6 (c).
Embodiment 4 PPy and SnO
2hybrid material air-sensitive performance test procedure
Getting a little testing sample (~ 5mg) puts into agate and grinds glass, after fully grinding, with distilled water furnishing pasty state, spread upon long 4 millimeters, have on the alumina ceramic tube of platinum filament lead-in wire, then nickel-chromium heater strip is penetrated in alumina ceramic tube, platinum filament and heater strip are welded in respectively on the corresponding position of six pin bases, finally explosion-proof net is fixed on to moulding on base.The gas sensor preparing is inserted on the wiring board of air-sensitive tester, under 90 ℃ of working temperatures, switches on and stablize after 48 hours, measure its air-sensitive performance.
The HW-30A type gas sensor tester that adopts Henan Hanwei Electronics Co., Ltd to produce in experiment carries out air-sensitive performance test.This system adopts voltage test method to carry out air-sensitive test, and basic test principle is shown in Fig. 5.V
cloop voltage, i.e. test voltage, in test, choosing test voltage is 5V; V
hheater voltage, by regulating different heater voltage values can provide gas sensor required working temperature; R
lbeing the pull-up resistor of connecting with gas sensor, is interchangeable card insert type, according to experiment, needs to choose different resistances; V
outpull-up resistor R
lon voltage.Air-sensitive instrument connection computer uses, and that on the screen of computer, show is V
out～Time (s) working curve.
By a series of PPy and SnO
2hybrid material is made thick-film type heater-type gas sensor one by one, at 90 ℃, tests its air-sensitive performance to ethanol, hydrogen, carbon monoxide, ammonia.
Gas sensing property test is found, the PPy of different polypyrrole content and SnO
2hybrid material does not all have gas sensing property to hydrogen, carbon monoxide, ammonia in the time of 90 ℃; Only alcohol gas is shown to good air-sensitive performance, sensitivity increases and increases gradually with gas concentration.This explanation, PPy prepared by hydrothermal method and SnO
2the gas sensor that hybrid material is made has good selectivity, response recovery time and lower working temperature (90 ℃) faster to ethanol, can get rid of the interference of hydrogen, carbon monoxide, ammonia gas simultaneously, is suitable for the detection to ethanol.With the standby PPy of mechanical blending legal system and SnO
2hybrid material does not but have gas sensing property to ethanol, and this illustrates that different preparation methods has impact significantly to the selectivity of sample.The PPy that mechanical blending legal system is standby and SnO
2hybrid material is applicable to the detection of ammonia, hydrogen sulfide and nitrogen oxide type toxic gas, and is not subject to the interference of alcohol gas; And with the standby PPy of hydro-thermal legal system and SnO
2hybrid material is more suitable for the detection of the organic volatile compounds of ethanol class.
Claims (1)
1. a method of preparing polypyrrole and tindioxide hybrid material, is characterized in that comprising the following steps:
(1) get 1 ~ 20mg pyrrole monomer, 80 ~ 99mg tindioxide, 3.4 ~ 68mg ammonium persulphate, 40 ~ 60ml water, be mixed in proportion, stirring, ultrasonic 30min;
(2) mixture is proceeded to reactor, and reactor is placed in to 140 ℃ of baking ovens, hydro-thermal reaction 8 hours, react complete, take out reactor, naturally cool to room temperature, by sedimentation and filtration, use respectively deionized water, ethanol, washing with acetone for several times, finally product is dried in 60 ℃ of baking ovens, obtain polypyrrole and tindioxide hybrid material.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600263A (en) * | 2015-01-05 | 2015-05-06 | 武汉理工大学 | SnO2@PPy interconnection nano-sheet structural material as well as preparation method and application thereof |
| CN107764871A (en) * | 2017-01-11 | 2018-03-06 | 郑州大学 | To NOXPPy/SnO with high selectivity2Nanotube composite air-sensitive material |
| CN108400300A (en) * | 2018-02-11 | 2018-08-14 | 长沙理工大学 | A kind of titanium dioxide/nitrogen-doped carbon cladding SnO2Combination electrode material and preparation method thereof |
| CN114002269A (en) * | 2021-11-01 | 2022-02-01 | 杭州电子科技大学 | polypeptide/MoS2/SnO2Preparation method and application of composite material |
-
2013
- 2013-10-17 CN CN201310485684.4A patent/CN103642040A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 耿丽娜等: "聚吡咯/二氧化锡杂化材料的制备及气敏性研究", 《无机化学学报》 * |
| 耿丽娜等: "聚苯胺/二氧化锡杂化材料的制备、表征及气敏性测试", 《无机化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600263A (en) * | 2015-01-05 | 2015-05-06 | 武汉理工大学 | SnO2@PPy interconnection nano-sheet structural material as well as preparation method and application thereof |
| CN107764871A (en) * | 2017-01-11 | 2018-03-06 | 郑州大学 | To NOXPPy/SnO with high selectivity2Nanotube composite air-sensitive material |
| CN107764871B (en) * | 2017-01-11 | 2020-08-25 | 郑州大学 | For NOXPPy/SnO with high selectivity2Nanotube composite gas sensitive material |
| CN108400300A (en) * | 2018-02-11 | 2018-08-14 | 长沙理工大学 | A kind of titanium dioxide/nitrogen-doped carbon cladding SnO2Combination electrode material and preparation method thereof |
| CN108400300B (en) * | 2018-02-11 | 2019-08-02 | 长沙理工大学 | A kind of titanium dioxide/nitrogen-doped carbon cladding SnO2Combination electrode material and preparation method thereof |
| CN114002269A (en) * | 2021-11-01 | 2022-02-01 | 杭州电子科技大学 | polypeptide/MoS2/SnO2Preparation method and application of composite material |
| CN114002269B (en) * | 2021-11-01 | 2023-11-24 | 杭州电子科技大学 | polypeptide/MoS 2 /SnO 2 Preparation method and application of composite material |
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Application publication date: 20140319 |