CN114989425A - Photochemical preparation method and application of lamellar polyaniline - Google Patents
Photochemical preparation method and application of lamellar polyaniline Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 35
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 34
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 10
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
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- 238000006731 degradation reaction Methods 0.000 abstract description 4
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- 238000004020 luminiscence type Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
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- 239000011521 glass Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 238000010586 diagram Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
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- 239000006185 dispersion Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
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- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
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- 238000005424 photoluminescence Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention belongs to the technical field of polyaniline preparation, and particularly relates to a photochemical preparation method and application of lamellar polyaniline. The method comprises the following steps: 1) dissolving aniline in dilute acid solution to obtain reaction precursor solution; 2) placing the reaction precursor solution obtained in the step 1) under ultraviolet irradiation for reaction, then filtering, and washing and drying the solid obtained by filtering to obtain lamellar polyaniline; the molar ratio of the aniline in the step 1) to the dilute acid solution is (0.25-2): 1; the dilute acid solution comprises more than one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid. The method is mild in reaction condition, easy to regulate and control, simple to operate and environment-friendly, the polyaniline with a regular morphology is prepared, a foundation is provided for the next application of the polyaniline, the method has excellent functions of photocatalytic hydrogen production, luminescence and organic dye degradation when being applied to preparation of the optical composite material, and the method has a good application prospect in the aspect of modifying semiconductor photocatalytic materials.
Description
Technical Field
The invention belongs to the technical field of polyaniline preparation, and particularly relates to a photochemical preparation method and application of lamellar polyaniline.
Background
Conductive polymers have been the focus of research since their appearance in 1960 because of their unique properties and the potential for numerous applications. Among conductive polymers, polyaniline is considered as a promising material, and has an extended pi-pi coupled electron system and a series of alternating single and double bond structures, which allows pi-electrons to be delocalized along the entire polymer chain, resulting in excellent electrical properties. Meanwhile, polyaniline is easy to synthesize, low in synthesis cost and superior to other conductive polymers. Therefore, the polyaniline can be widely applied to the fields of photocatalysis, gas sensors, solar cells and the like.
The existing polyaniline synthesis methods mainly comprise an oxidative polymerization method and an electric polymerization method, and the methods for preparing polyaniline by photochemical polymerization are relatively few.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a photochemical preparation method of lamellar polyaniline and applications thereof.
The technical content of the invention is as follows:
the invention provides a photochemical preparation method of lamellar polyaniline, which comprises the following steps:
1) dissolving aniline in dilute acid solution to obtain reaction precursor solution;
2) placing the reaction precursor solution obtained in the step 1) under ultraviolet irradiation for reaction, then filtering, and washing and drying the solid obtained by filtering to obtain lamellar polyaniline;
the molar ratio of the aniline to the dilute acid solution in the step 1) is (0.25-2): 1, preferably (0.25-1): 1;
the dilute acid solution comprises more than one of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, and is preferably dilute hydrochloric acid;
step 2), the wavelength of the ultraviolet light is one of 254nm and 365 nm, preferably 254 nm;
the irradiation time of the ultraviolet light is 6-24 hours, and preferably 12-24 hours;
the liquid surface radiation intensity of the ultraviolet light is 0.5-2 mW/cm 2 Preferably 1.5 mW/cm 2 ；
The washing adopts deionized water and absolute ethyl alcohol;
the drying condition is that the drying time is 6-24 hours at the temperature of 50-80 ℃.
The invention also provides the lamellar polyaniline prepared by the preparation method, wherein the polyaniline sheets are stacked to form lamellar polyaniline, and the length of the lamellar polyaniline is 600 nm-5 mu m.
The invention also provides application of the cadmium sulfide/polyaniline composite material taking laminar polyaniline as a substrate in photocatalysis.
The invention also provides application of the tin dioxide/polyaniline composite material with the laminar polyaniline as the substrate in photocatalysis.
The invention also provides application of the copper sulfide/polyaniline composite material with the laminar polyaniline as the substrate in photocatalysis.
The invention has the following beneficial effects:
the photochemical preparation method of the lamellar polyaniline has the advantages of mild reaction conditions, easy regulation and control, simple operation and environmental protection, prepares the polyaniline with regular morphology, provides a basis for the next application of the polyaniline, has excellent functions of producing hydrogen by photocatalysis, emitting light and degrading organic dyes when being applied to preparing a light composite material, and has good application prospect in the aspect of modifying semiconductor photocatalysis materials.
Drawings
FIG. 1 is a scanning electron micrograph of a polyaniline sheet of example 1;
FIG. 2 is an FTIR spectrum of the lamellar polyaniline of example 1;
FIG. 3 is a scanning electron micrograph of the composite of laminar polyaniline and cadmium sulfide of example 4;
FIG. 4 is a scanning electron micrograph of the layered polyaniline/tin dioxide composite material of example 5;
FIG. 5 is a graph of photocatalytic hydrogen production performance of the composite material of laminar polyaniline and cadmium sulfide of example 4 and the cadmium sulfide particles of comparative example 1;
FIG. 6 is a repeated diagram of photocatalytic hydrogen production of the composite material of laminar polyaniline and cadmium sulfide in example 4;
FIG. 7 is a repeated diagram of photocatalytic hydrogen production of cadmium sulfide particles of comparative example 1;
FIG. 8 is a graph of the photoluminescence performance of the composite of laminar polyaniline and cadmium sulfide of example 2, cadmium sulfide particles of comparative example 1, and laminar polyaniline;
FIG. 9 is a graph of the performance of the photocatalytic degradation methylene blue solution of the laminar polyaniline/tin dioxide composite material of example 5 and the tin dioxide particles of comparative example 2;
FIG. 10 is a diagram of the performance of photocatalytic degradation of rhodamine B for the laminar polyaniline and cadmium sulfide composite material of example 4 and the cadmium sulfide particles of comparative example 1;
FIG. 11 is a diagram of the photocatalytic degradation of rhodamine B of the lamellar polyaniline copper sulfide composite material of example 6.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
Photochemical preparation method of lamellar polyaniline
1) Dissolving 0.01 moL of aniline in 30 mL of 1M dilute hydrochloric acid solution, and stirring for 30 min to obtain reaction precursor solution;
2) adding the reaction precursor solution obtained in the step 1) into a 250 mL quartz conical flask, adding a magnetic stirrer, controlling the stirring speed at 100 r/min, placing ultraviolet lamps (8W 254 nm) at two sides of the quartz flask, and adjusting the light intensity to 1.5 mW/cm 2 Carrying out ultraviolet radiation for 24 hours, then filtering, washing and washing the solid obtained by filtering to be neutral by using absolute ethyl alcohol and deionized water, and finally, placing the solid in an oven to be dried for 12 hours at the temperature of 60 ℃ to obtain lamellar polyaniline;
as shown in fig. 1, a clear lamellar structure is visible in a scanning electron micrograph of the obtained polyaniline.
As shown in FIG. 2, the FTIR spectrum of the obtained polyaniline is 1572 cm -1 ，1500 cm -1 ，1287 cm -1 ，798 cm -1 The peaks at (a) correspond to C = N, C = C, C-N, N-H of polyaniline, respectively, demonstrating the presence of polyaniline.
Example 2
Photochemical preparation method of lamellar polyaniline
1) Dissolving 0.01 moL of aniline in 25 mL of 1M dilute sulfuric acid solution, and stirring for 30 min to obtain a reaction precursor solution;
2) adding the reaction precursor solution obtained in the step 1) into a 250 mL quartz conical flask, adding a magnetic stirrer, controlling the stirring speed at 100 r/min, placing ultraviolet lamps (8W 254 nm) at two sides of the quartz flask, and adjusting the light intensity to be 2 mW/cm 2 And (3) carrying out ultraviolet radiation for 24 hours, then filtering, washing and washing the solid obtained by filtering to be neutral by using absolute ethyl alcohol and deionized water, and finally, placing the solid in an oven to dry for 20 hours at 50 ℃ to obtain the lamellar polyaniline.
Example 3
Photochemical preparation method of lamellar polyaniline
1) Dissolving 0.01 moL of aniline in 10 mL of 1M dilute nitric acid solution, and stirring for 30 min to obtain reaction precursor solution;
2) adding the reaction precursor solution obtained in the step 1) into a 250 mL quartz conical flask, adding a magnetic stirrer, controlling the stirring speed at 100 r/min, placing ultraviolet lamps (8W 365 nm) at two sides of the quartz flask, and adjusting the light intensity to be 0.5 mW/cm 2 Carrying out ultraviolet radiation for 12 h, then filtering, washing and washing the solid obtained by filtering to be neutral by using absolute ethyl alcohol and deionized water, and finally placing the solid in an oven to be dried for 6 h at the temperature of 80 ℃ to obtain the lamellar polyaniline.
Example 4
Laminar polyaniline/cadmium sulfide composite material
1) Dissolving 0.0075 moL of cadmium sulfate and 0.005 moL of sodium thiosulfate in 30 mL of deionized water, dropwise adding 20mL of absolute ethyl alcohol in the ultrasonic process, adding 20 mg of laminar polyaniline of example 1, and continuing to perform ultrasonic dispersion for 15 min to obtain a reaction mixed solution;
2) adding the reaction mixed solution obtained in the step 3) into a 100 mL surface dish, adding a magnetic stirring rotor, controlling the stirring speed at 100 r/min, covering a preservative film on the surface dish, transferring the preservative film to an ultraviolet lamp (with the power of 16W and the wavelength of 254 nm), adjusting the height of the liquid level of the reaction mixed solution from a light source to be 3.4 cm, irradiating the liquid by the ultraviolet lamp for 24h, filtering, washing the filtered solid by deionized water for 4 times, and then placing the solid in a 60 ℃ oven for drying for 12 h to obtain the lamellar polyaniline/cadmium sulfide composite material, wherein a scanning electron microscope image of the lamellar polyaniline/cadmium sulfide composite material is shown in fig. 3.
Example 5
Lamellar polyaniline/tin dioxide composite material
1) 0.50g SnSO was weighed 4 Dissolved in 100 mL of 5.00g/L H 2 SO 4 In the method, 0.05 g of the polyaniline powder of the embodiment 1 is added to the precursor, and the polyaniline is fully dispersed, so that SnSO in the precursor solution 4 /H 2 SO 4 The mass ratio of the PANI/PANI is 1:10: 0.1;
2) placing the dispersion system obtained in the step 1) under an ultraviolet lamp for illumination, adjusting the height of the ultraviolet lamp tube, and controlling the ultraviolet light intensity of the liquid level to be 0.70 mW/cm 2 And after 24 hours, centrifugally separating and collecting the precipitate, repeatedly washing the precipitate to be neutral by using deionized water, and drying the precipitate at 60 ℃ for 6 hours to obtain SnO prepared by photochemical reaction 2 The scanning electron microscope image of the/PANI composite material is shown in FIG. 4.
Example 6
Laminar polyaniline/copper sulfide composite material
1) Accurately weighing 0.02 moL CuSO 4 And 0.01 moL Na 2 S 2 O 3 Dissolving the polyaniline powder in 100 mL of deionized water, adding 20 mg of the polyaniline powder in the embodiment 1 after the polyaniline powder is completely dissolved, and performing ultrasonic treatment for 30 min to obtain a reaction mixed solution;
2) placing the dispersion system obtained in the step 1) under an ultraviolet lamp for illumination, adjusting the height of an ultraviolet lamp tube, and controlling the ultraviolet light intensity of the liquid level to be 0.70 mW/cm 2 And after 24 hours, carrying out centrifugal separation to collect precipitate, repeatedly washing the precipitate with deionized water to be neutral, and drying at 70 ℃ for 12 hours to obtain the CuS/PANI composite material prepared by photochemical reaction.
Comparative example 1
Photochemical preparation of cadmium sulfide particles
1) Dissolving 0.0075 mol of cadmium sulfate and 0.005 mol of sodium thiosulfate in 30 mL of deionized water, dropwise adding 20mL of absolute ethyl alcohol in the ultrasonic process, and continuing to perform ultrasonic dispersion for 15 min after the addition is finished to obtain a reaction mixed solution;
2) adding the reaction mixed solution obtained in the step 1) into a 100 mL watch glass, adding a magnetic stirring rotor, controlling the stirring speed at 100 r/min, covering a preservative film on the watch glass, transferring the watch glass to an ultraviolet lamp (with the power of 16W and the wavelength of 254 nm), adjusting the height of the liquid level of the reaction mixed solution from a light source to be 3.4 cm, irradiating the liquid by the ultraviolet lamp for 24h, filtering, washing the filtered solid by deionized water for 4 times, and then placing the washed solid in a 60 ℃ oven for drying for 12 h to obtain cadmium sulfide particles.
Comparative example 2
Photochemical preparation of stannic oxide particles
0.50g SnSO was weighed 4 Dissolved in 100 mL of 5.00g/L H 2 SO 4 Obtaining reaction precursor liquid, adjusting the height of an ultraviolet lamp tube, and controlling the ultraviolet light intensity of the liquid level to be 0.70 mW/cm 2 And after 24 hours, centrifugally separating and collecting the precipitate, repeatedly washing the precipitate to be neutral by using deionized water, and drying the precipitate at 60 ℃ for 6 hours to obtain SnO prepared by photochemical reaction 2 And (3) granules.
The products obtained in the above examples and comparative examples were subjected to the following performance tests:
test example 1
And (3) photocatalytic hydrogen production test:
the photocatalytic hydrogen production experiment is carried out in a gas closed side irradiation system, and a 50W LED blue lamp with the wavelength of 452nm is used as a light source. Weighing 3.15 g of anhydrous sodium sulfite and 8.2 g of sodium sulfide, putting the anhydrous sodium sulfite and the sodium sulfide into a 200 ml glass beaker, adding 100 ml of deionized water for dissolving, after the solid is completely dissolved, weighing 0.02 g of the cadmium sulfide photocatalytic material composite material, putting the cadmium sulfide photocatalytic material composite material into the beaker, carrying out ultrasonic treatment for 10min until the composite material is fully dispersed, then transferring a dispersion system into a reactor, completely degassing within about 30 min, and then irradiating by using a blue light lamp. The hydrogen production rate was determined by an on-line gas chromatograph (thermal conductivity detector (TCD), nitrogen as carrier gas, 5A molecular sieve column). Light was sampled every 0.5 h for 2 h and data was recorded. The hydrogen generation amount (mmol/g) was calculated by a standard curve and an ideal gas equation of state formula. The comparison graph of the photocatalytic hydrogen production performance of the laminar polyaniline/cadmium sulfide composite material of the example 4 and the cadmium sulfide particles of the comparative example 1 is shown in fig. 5, and it can be seen from the graph that the performance of the laminar polyaniline/cadmium sulfide composite material of the example 4 is better than that of the single-component cadmium sulfide of the comparative example 1, which shows that the polyaniline can promote the photocatalytic performance of the cadmium sulfide and is applied to the field of photocatalysis.
The results of continuous photocatalytic hydrogen production tests on the laminar polyaniline/cadmium sulfide composite material and the single-component cadmium sulfide of comparative example 1 are shown in fig. 6 and 7. From fig. 6, it can be seen that the lamellar polyaniline/cadmium sulfide composite material can be recycled for 4 cycles, the photocatalytic performance of the material is not reduced during recycling, and the performance of the single-component cadmium sulfide of comparative example 1 shown in fig. 7 is only 49% of the initial performance after 3 cycles, which indicates that the lamellar PANI can effectively improve the stability of the cadmium sulfide to inhibit photo-corrosion.
Test example 2
PL test:
photoluminescence tests were performed on the laminar polyaniline/cadmium sulfide composite material, the single component cadmium sulfide of comparative example 1, and the laminar polyaniline, and the results are shown in fig. 8. The fluorescence emission intensity of the lamellar polyaniline/cadmium sulfide composite material is obviously lower than that of a single component, which shows that the addition of PANI can effectively separate photon-generated carriers and reduce the loss of photon-generated electrons.
Test example 3
Photocatalytic degradation of organic dyes:
0.02 g of the polyaniline/tin dioxide composite in laminar form of example 5 was placed in a 200 mL glass beaker, and 100 mL of 1.90X 10 composite was added −5 Subjecting the RhB solution of mol/L to ultrasonic treatment at room temperature, placing in dark for reaction for 30 min, taking out 5 mL of reaction sample, centrifuging, filtering, collecting supernatant, and measuring original absorbance C at wavelength of 553 nm (corresponding to maximum absorption coefficient of RhB here) 0 And (3) putting the taken sample back into the beaker, putting the beaker under an ultraviolet lamp (8W, 254 nm) for irradiation reaction (the ultraviolet lamp is arranged on the top of the beaker), taking the sample 1 time every 20 min of irradiation, centrifuging and filtering the sample, taking supernatant, and measuring the absorbance C at the wavelength of 553 nm.
The results are shown in FIG. 9, for comparative example 2, a single group of SnO 2 The degradation rate of RhB under the irradiation of ultraviolet light for 80min is 78 percent,in example 5, the lamellar polyaniline/tin dioxide composite material is degraded by 90% in 80min, which shows that the photocatalytic activity of tin dioxide can be improved by adding lamellar polyaniline.
Test example 4
Photocatalytic degradation of organic dyes:
0.02 g of the polyaniline/cadmium sulfide composite in laminar form of example 4 was placed in a 200 mL glass beaker, and 100 mL of 1.90X 10 −5 Subjecting the RhB solution of mol/L to ultrasonic treatment at room temperature, placing in dark for reaction for 30 min, taking out 5 mL of reaction sample, centrifuging, filtering, collecting supernatant, and measuring original absorbance C at wavelength of 553 nm (corresponding to maximum absorption coefficient of RhB here) 0 Placing the sample back into the beaker, placing the beaker under an LED blue light lamp (50W, 452 nm) for irradiation reaction (the blue light lamp is arranged at the top of the beaker), taking the sample 1 time every 20 min of irradiation, taking supernatant after centrifugal filtration, and measuring the absorbance C at the wavelength of 553 nm;
the result is shown in fig. 10, the degradation rate of RhB of the single group of CdS in comparative example 1 under the irradiation of a blue light lamp for 80min is 76%, while the degradation rate of the laminar polyaniline cadmium sulfide composite material in example 4 is 92% in 80min, which indicates that the photocatalytic activity of cadmium sulfide can be improved by adding the laminar polyaniline.
Test example 5
Photocatalytic degradation of organic dyes:
0.02 g of the polyaniline/copper sulfide composite in the form of a sheet of example 6 was placed in a 200 mL glass beaker, and 100 mL of the composite was added at 1.90X 10 −5 mol/L RhB solution and 0.5 mL of 3% H 2 O 2 Subjecting the mixture to ultrasonic homogenization at room temperature, reacting in the dark for 30 min, taking out 5 mL of reaction sample, centrifuging, filtering, collecting supernatant, and measuring the original absorbance C at a wavelength of 553 nm (where the maximum absorption coefficient corresponds to RhB) 0 Placing the sample into a beaker, placing the beaker under two ultraviolet lamps (8W, 254 nm) for irradiation reaction (the ultraviolet lamps are arranged on the top of the beaker), taking the sample 1 time every 20 min of irradiation, centrifuging and filtering to obtain supernatant, and measuring the absorbance C at the wavelength of 553 nm.
The results are shown in FIG. 11, and example 6 is a curing process of lamellar polyanilineCopper composite material in H 2 O 2 With the assistance of the method, RhB can be effectively degraded, and is degraded by 90% in 140 min.
The above embodiments are only examples of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. A photochemical preparation method of lamellar polyaniline is characterized by comprising the following steps:
1) dissolving aniline in dilute acid solution to obtain reaction precursor solution;
2) placing the reaction precursor solution obtained in the step 1) under ultraviolet irradiation for reaction, then filtering, and washing and drying the solid obtained by filtering to obtain the lamellar polyaniline.
2. The photochemical preparation method of a lamellar polyaniline according to claim 1, characterized in that the molar ratio of aniline to dilute acid solution in step 1) is (0.25-2): 1.
3. the photochemical preparation method of a laminar polyaniline of claim 1, characterized in that the dilute acid solution of step 1) comprises one or more of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid.
4. The method for photochemical preparation of a lamellar polyaniline according to claim 1, characterized in that the wavelength of the ultraviolet light of step 2) is one of 254nm and 365 nm.
5. The photochemical preparation method of the laminar polyaniline according to claim 1, wherein the irradiation time of the ultraviolet light in step 2) is 6 to 24 hours.
6. Photochemical preparation of the laminar polyaniline according to claim 1The preparation method is characterized in that the liquid surface radiation intensity of the ultraviolet light in the step 2) is 0.5-2 mW/cm 2 。
7. The lamellar polyaniline prepared by the preparation method according to any one of claims 1 to 6, wherein the polyaniline is stacked between sheets to form lamellar.
8. The application of the cadmium sulfide/polyaniline composite material taking the laminar polyaniline as the substrate according to claim 7 in photocatalysis.
9. The use of the tin dioxide/polyaniline composite material based on the laminar polyaniline of claim 7 in photocatalysis.
10. The application of the copper sulfide/polyaniline composite material taking the laminar polyaniline as the substrate according to claim 7 in photocatalysis.
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