CN114985003B - Preparation method and application of chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film - Google Patents
Preparation method and application of chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 58
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 45
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 12
- 239000000460 chlorine Substances 0.000 title claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000010355 oscillation Effects 0.000 claims abstract description 38
- 239000011521 glass Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 23
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 241000579895 Chlorostilbon Species 0.000 claims description 5
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- 239000010976 emerald Substances 0.000 claims description 5
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- 239000002131 composite material Substances 0.000 abstract description 13
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- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 4
- 235000019366 oxytetracycline Nutrition 0.000 description 4
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- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 4
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 3
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- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
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- RXZBMPWDPOLZGW-XMRMVWPWSA-N (E)-roxithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=N/OCOCCOC)/[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 RXZBMPWDPOLZGW-XMRMVWPWSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 229940042040 innovative drug Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
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- 229960002180 tetracycline Drugs 0.000 description 1
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- 150000003522 tetracyclines Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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Abstract
The invention discloses a preparation method and application of a chlorine doped cuprous oxide/polyaniline/ITO photocatalysis film, which specifically comprises the following steps: sequentially adding the ITO conductive glass sheet into acetone, ethanol and deionized water, carrying out ultrasonic oscillation, and drying; immersing ITO conductive glass sheet into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, adding ammonium persulfate-hydrochloric acid aqueous solution for polymerization reaction, cleaning, drying, finally immersing PANI/ITO film into copper acetate solution, adding NaOH solution and hydroxylamine hydrochloride aqueous solution for reaction, washing, drying to obtain Cl-Cu 2 O/PANI/ITO photocatalytic film. Cl-Cu of the invention 2 The O/PANI/ITO composite photocatalytic film can realize higher efficient photocatalytic efficiency by the formed p-n heterojunction. The photocatalytic film is mainly applied to degradation of organic pollutants in water, has recoverability, does not pollute the water and can be recycled.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to a preparation method of a chlorine-doped cuprous oxide/polyaniline/ITO photocatalytic film and application of the photocatalytic film.
Background
With the continuous improvement of the human science and technology level and the rapid development of the medical level, innovative drugs such as various novel antibiotics and the like begin to appear in the human visual field, and people begin to survive the pain and even death caused by many diseases, but the influence of the novel antibiotics and the like is ignored. The wastewater produced by the production of the antibiotics in pharmaceutical factories often selects conventional wastewater treatment means such as a chemical treatment method, a heat treatment method, a Fenton method and the like, but the wastewater is often high in material resources and financial resources, and the wastewater is not efficient and even causes secondary pollution due to the addition of other chemical agents. The occurrence rate of the drug resistance genes of the antibiotics in nature is greatly improved due to the large discharge of the antibiotics. Therefore, it is important to design a novel, efficient, green and pollution-free sewage treatment technology.
Disclosure of Invention
The invention aims to provide a preparation method of a chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film, which not only can rapidly transfer photogenerated carriers to degrade organic pollutant molecules, but also can improve the recoverability and the recycling rate of the film.
The invention further aims to provide an application of the chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film in degrading organic pollutants in water.
The technical scheme adopted by the invention is that the preparation method of the chlorine doped cuprous oxide/polyaniline/ITO photocatalysis film is implemented according to the following steps:
step 1, adding an ITO conductive glass sheet into an acetone solvent for ultrasonic oscillation, then adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, and finally adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation and drying;
step 2, vertically immersing the ITO conductive glass sheet obtained in the step 1 into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, slowly adding ammonium persulfate-hydrochloric acid aqueous solution into aniline-hydrochloric acid aqueous solution for polymerization reaction, washing with deionized water and ethanol, and drying to obtain a PANI/ITO film with an emerald polyaniline film on the surface;
step 3, vertically placing the PANI/ITO film in a copper acetate solution, respectively adding a NaOH solution and a hydroxylamine hydrochloride aqueous solution for stirring reaction, washing for a plurality of times by deionized water, and drying to obtain Cl-Cu 2 O/PANI/ITO photocatalytic film.
The present invention is also characterized in that,
in the step 1, the ultrasonic oscillation time is 10-30min each time; the drying temperature was 60℃and the drying time was 12 hours.
In the step 2, the concentration of aniline in the aniline-hydrochloric acid aqueous solution is 0.05-0.1mol/L, and the concentration of hydrochloric acid is 1mol/L; the concentration of ammonium persulfate in the ammonium persulfate-hydrochloric acid aqueous solution is 0.025-0.15mol/L.
In the step 2, the ultrasonic oscillation time is 10-30min; the polymerization reaction temperature is 0 ℃, and the polymerization reaction time is 60-120min; the drying temperature was 70℃and the drying time was 12 hours.
In the step 3, the concentration of the copper acetate solution is 0.1mol/L; the concentration of the NaOH solution is 1mol/L; the concentration of the hydroxylamine hydrochloride aqueous solution is 0.5-2.5mol/L.
In the step 3, the soaking time is 20min; the reaction time is 60-90min; the drying temperature was 70℃and the drying time was 12 hours.
The beneficial effects of the invention are as follows: cl-Cu constructed by the invention 2 The O/PANI/ITO composite photocatalytic film can realize higher efficient photocatalytic efficiency by the formed p-n heterojunction. The photocatalytic film has recoverability, does not pollute the water body and can be reused. In addition, the adopted raw materials are simple and easy to obtain, the preparation process is simple, and the industrialized mass production can be realized.
Drawings
FIG. 1 is a Cl-Cu film prepared in example 1 2 UV-Vis DRS absorption spectrum of the O/PANI/ITO composite photocatalytic film CPI-1;
FIG. 2 is a Cl-Cu film prepared in example 1 2 Photon energy hν sum (αhν) of O/PANI/ITO composite photocatalytic film CPI-1 2 A curve;
FIG. 3 is a Cl-Cu film prepared in example 1 2 Photocatalytic degradation curve graph of the O/PANI/ITO composite photocatalytic film CPI-1;
FIG. 4 is a Cl-Cu film prepared in example 2 2 Photocatalytic degradation curve graph of the O/PANI/ITO composite photocatalytic film CPI-2;
FIG. 5 is a Cl-Cu film prepared in example 3 2 Photocatalytic degradation curve graph of the O/PANI/ITO composite photocatalytic film CPI-3;
FIG. 6 is a graph of Cl-Cu prepared in examples 1-3 2 And (3) photocatalytic degradation rate curves of the O/PANI/ITO composite photocatalytic films CPI-1, CPI-2 and CPI-3.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention discloses a preparation method of a chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film, which is implemented according to the following steps:
step 1, adding an ITO conductive glass sheet with the size of 2 multiplied by 4cm into an acetone solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation, and finally drying the treated ITO conductive glass sheet in an oven;
the ultrasonic oscillation time is 10-30min each time;
the drying temperature is 60 ℃ and the drying time is 12 hours;
step 2, vertically immersing the ITO conductive glass sheet obtained in the step 1 into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, slowly adding ammonium persulfate-hydrochloric acid aqueous solution into aniline-hydrochloric acid aqueous solution for polymerization reaction, washing with deionized water and ethanol, and drying in an oven to obtain a PANI/ITO film with an emerald green polyaniline film on the surface;
the concentration of aniline in the aniline-hydrochloric acid aqueous solution is 0.05-0.1mol/L, and the concentration of hydrochloric acid is 1mol/L;
the ultrasonic oscillation time is 10-30min;
the concentration of ammonium persulfate in the ammonium persulfate-hydrochloric acid aqueous solution is 0.025-0.15mol/L; the concentration of hydrochloric acid is 1mol/L;
the polymerization reaction temperature is 0 ℃, and the polymerization reaction time is 60-120min;
the drying temperature is 70 ℃ and the drying time is 12 hours;
step 3, vertically placing the PANI/ITO film in a copper acetate solution, respectively adding a NaOH solution and a hydroxylamine hydrochloride aqueous solution for stirring reaction, washing for a plurality of times by deionized water, and drying to obtain Cl-Cu 2 O/PANI/ITO (chlorine doped cuprous oxide/polyaniline/ITO) photocatalytic film;
the soaking time is 20min;
the concentration of the copper acetate solution is 0.1mol/L; the concentration of the NaOH solution is 1mol/L; the concentration of the hydroxylamine hydrochloride aqueous solution is 0.5-2.5mol/L;
the reaction time is 60-90min; the drying temperature was 70℃and the drying time was 12 hours.
The invention takes ITO conductive glass as a substrate material, and a large amount of silicon hydroxyl groups existing on the surface of the ITO conductive glass can be used as active sites to grow a layer of emerald polyaniline film and some Cu in situ in two steps 2 O nanoparticles. P-type semiconductor polyaniline and n-type semiconductor Cl-Cu on ITO conductive glass 2 O nano particles form a p-n heterojunction, the generation of the heterojunction can form a built-in electric field, and the built-in electric field exists in the presence of the built-in electric field and the p-type semiconductor Cl-Cu 2 The photo-generated holes generated by the O nano particles can be quickly transferred to the P-type semiconductor polyaniline film, and the photo-generated electrons generated by polyaniline can be transferred to Cl-Cu 2 O, thereby greatly accelerating the separation efficiency of photo-generated electrons and holes and generating more photo-generated carriers to realize the efficient degradation of organic pollutants in the water body. The material is different from pure particle type photocatalyst, and can be recycled for multiple times.
The photocatalytic film of the invention can be mainly applied to degradation of organic pollutants in water, such as antibiotics including tetracycline, aureomycin, roxithromycin, norfloxacin and the like; examples of the dye include methylene blue, methylene orange, congo red, etc.
Example 1
The invention discloses a preparation method of a chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film, which is implemented according to the following steps:
step 1, adding an ITO conductive glass sheet with the size of 2 multiplied by 4cm into an acetone solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation, and finally drying the treated ITO conductive glass sheet in an oven;
the ultrasonic oscillation time is 30min each time;
the drying temperature is 60 ℃ and the drying time is 12 hours;
step 2, 50mL of mixed aqueous solution of aniline and hydrochloric acid is taken, and the concentration of the hydrochloric acid is 1mol/L; the aniline concentration was 0.05mol/L. Vertically immersing the ITO conductive glass sheet obtained in the step 1 into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation; placing the solution in an ice bath container, and then taking 50mL of an aqueous solution of ammonium persulfate and hydrochloric acid, wherein the concentration of the hydrochloric acid is 1mol/L; the concentration of ammonium persulfate is 0.05mol/L; slowly adding ammonium persulfate-hydrochloric acid aqueous solution into aniline-hydrochloric acid aqueous solution for polymerization reaction, washing with deionized water and ethanol, and drying in an oven to obtain a PANI/ITO film with an emerald polyaniline film on the surface;
the ultrasonic oscillation time is 10min;
the polymerization temperature is 0 ℃ and the polymerization time is 90min;
the drying temperature is 70 ℃ and the drying time is 12 hours;
step 3, preparing 100mL of 0.1mol/L copper acetate solution, vertically placing the PANI/ITO film into the soaked copper acetate solution, respectively adding 35mL of NaOH aqueous solution (1 mol/L) and 17.5mL of hydroxylamine hydrochloride aqueous solution (2 mol/L) into the copper acetate solution, stirring and reacting for 60min, washing for several times with deionized water, and drying at 70 ℃ for 12h to obtain the productTo Cl-Cu 2 O/PANI/ITO photocatalytic film; the photocatalytic film is marked as CPI-1, oxytetracycline is taken as a target degradation product, and the degradation effect of the material on oxytetracycline is analyzed.
Example 2
The invention discloses a preparation method of a chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film, which is implemented according to the following steps:
step 1, adding an ITO conductive glass sheet with the size of 2 multiplied by 4cm into an acetone solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation, and finally drying the treated ITO conductive glass sheet in an oven;
the ultrasonic oscillation time is 20min each time;
the drying temperature is 60 ℃ and the drying time is 12 hours;
step 2, 50mL of mixed aqueous solution of aniline and hydrochloric acid is taken, and the concentration of the hydrochloric acid is 1mol/L; the concentration of aniline is 0.05mol/L, the ITO conductive glass sheet obtained in the step 1 is vertically immersed into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, the solution is placed in an ice bath container, 50mL of aqueous solution of ammonium persulfate and hydrochloric acid with certain concentration is prepared, and the concentration of hydrochloric acid is 1mol/L; ammonium persulfate concentration is 0.0625mol/L, then ammonium persulfate-hydrochloric acid aqueous solution is slowly added into aniline-hydrochloric acid aqueous solution for polymerization reaction, deionized water and ethanol are used for cleaning, and the mixture is placed in an oven for drying, so that a PANI/ITO film with an emerald green polyaniline film on the surface is obtained;
the ultrasonic oscillation time is 20min;
the polymerization temperature is 0 ℃, and the polymerization time is 120min;
the drying temperature is 70 ℃ and the drying time is 12 hours;
step 3, preparing 100mL of 0.1mol/L copper acetate solution, vertically placing the PANI/ITO film into the soaked copper acetate solution, respectively adding 35mL of NaOH aqueous solution (1 mol/L) and 17.5mL of hydroxylamine hydrochloride aqueous solution (2 mol/L) into the copper acetate solution, stirring and reacting for 60min, washing with deionized water for several times, and drying to obtain Cl-Cu 2 O/PANI/ITO photocatalytic filmThe method comprises the steps of carrying out a first treatment on the surface of the The photocatalytic film is marked as CPI-2, oxytetracycline is taken as a target degradation product, and the degradation effect of the material on oxytetracycline is analyzed.
Example 3
The invention discloses a preparation method of a chlorine doped cuprous oxide/polyaniline/ITO photocatalytic film, which is implemented according to the following steps:
step 1, adding an ITO conductive glass sheet with the size of 2 multiplied by 4cm into an acetone solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation, and finally drying the treated ITO conductive glass sheet in an oven;
the ultrasonic oscillation time is 30min each time;
the drying temperature is 60 ℃ and the drying time is 12 hours;
step 2, preparing 50mL of mixed aqueous solution of aniline and hydrochloric acid with a certain concentration, wherein the concentration of the hydrochloric acid is 1mol/L; the aniline concentration was 0.05mol/L. Vertically immersing the ITO conductive glass sheet obtained in the step 1 into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, placing the solution into an ice bath container, and then preparing 50mL of aqueous solution of ammonium persulfate and hydrochloric acid with a certain concentration, wherein the concentration of hydrochloric acid is 1mol/L; the concentration of ammonium persulfate was 0.025mol/L. Slowly adding ammonium persulfate-hydrochloric acid aqueous solution into aniline-hydrochloric acid aqueous solution for polymerization reaction, washing with deionized water and ethanol, and drying in an oven to obtain a PANI/ITO film with an emerald polyaniline film on the surface;
the ultrasonic oscillation time is 10min;
the polymerization temperature is 0 ℃ and the polymerization time is 90min;
the drying temperature is 70 ℃ and the drying time is 12 hours;
step 3, preparing 100mL of copper acetate solution with the concentration of 0.1mol/L, vertically placing the PANI/ITO film into the soaked copper acetate solution, respectively adding 35mL of NaOH aqueous solution (1 mol/L) and 17.5mL of hydroxylamine hydrochloride aqueous solution (1.5 mol/L) into the copper acetate solution, stirring and reacting for 60min, washing with deionized water for several times, and drying to obtain Cl-Cu 2 O/PANI/ITO photocatalytic film; marking the photocatalytic filmAnd taking the terramycin as a target degradation product for CPI-3, and analyzing the degradation effect of the material on terramycin.
FIGS. 1 and 2 are, respectively, cl-Cu prepared in example 1 2 UV-Vis DRS absorption spectrum of O/PANI/ITO composite photocatalytic film CPI-1 and photon energy hν sum (alpha h ν) 2 FIGS. 3-5 are graphs of Cl-Cu prepared in examples 1-3, respectively 2 Photocatalytic degradation curves of the O/PANI/ITO composite photocatalytic films CPI-1, CPI-2 and CPI-3. FIG. 6 is a graph of Cl-Cu prepared in examples 1-3 2 And (3) photocatalytic degradation rate curves of the O/PANI/ITO composite photocatalytic films CPI-1, CPI-2 and CPI-3. From the UV-Vis DRS absorption spectrum, the absorbance of the composite photocatalytic film is rapidly increased at 600nm, the maximum value is reached at 460nm, and the photon energy hν and (alpha h ν) are calculated 2 The bandgap was found to be 2.33eV. Cl-Cu 2 The degradation performance of the O/PANI/ITO composite photocatalytic film is analyzed, and the degradation rates of CPI-1, CPI-2 and CPI-3 on terramycin are 79.4%, 76.6% and 82.5%, respectively. Therefore, the material is fully proved to have very good photocatalytic degradation performance.
Claims (4)
1. The preparation method of the chlorine doped cuprous oxide/polyaniline/ITO photocatalysis film is characterized by comprising the following steps of:
step 1, adding an ITO conductive glass sheet into an acetone solvent for ultrasonic oscillation, then adding the ITO conductive glass sheet into an ethanol solvent for ultrasonic oscillation, and finally adding the ITO conductive glass sheet into deionized water for ultrasonic oscillation and drying;
step 2, vertically immersing the ITO conductive glass sheet obtained in the step 1 into aniline-hydrochloric acid aqueous solution for ultrasonic oscillation, slowly adding ammonium persulfate-hydrochloric acid aqueous solution into aniline-hydrochloric acid aqueous solution for polymerization reaction, washing with deionized water and ethanol, and drying to obtain a PANI/ITO film with an emerald polyaniline film on the surface;
the concentration of aniline in the aniline-hydrochloric acid aqueous solution is 0.05-0.1mol/L, and the concentration of hydrochloric acid is 1mol/L; the concentration of ammonium persulfate in the ammonium persulfate-hydrochloric acid aqueous solution is 0.025-0.15mol/L;
the ultrasonic oscillation time is 10-30min; the polymerization reaction temperature is 0 ℃, and the polymerization reaction time is 60-120min; the drying temperature is 70 ℃ and the drying time is 12 hours;
step 3, vertically placing the PANI/ITO film in a copper acetate solution, respectively adding a NaOH solution and a hydroxylamine hydrochloride aqueous solution for stirring reaction, washing for a plurality of times by deionized water, and drying to obtain Cl-Cu 2 O/PANI/ITO photocatalytic film;
the concentration of the copper acetate solution is 0.1mol/L; the concentration of the NaOH solution is 1mol/L; the concentration of the hydroxylamine hydrochloride aqueous solution is 0.5-2.5mol/L.
2. The method for preparing the chlorine-doped cuprous oxide/polyaniline/ITO photocatalytic film according to claim 1, wherein in the step 1, the ultrasonic oscillation time is 10-30min each time; the drying temperature was 60℃and the drying time was 12 hours.
3. The method for preparing the chlorine-doped cuprous oxide/polyaniline/ITO photocatalytic film according to claim 1, wherein in the step 3, the soaking time is 20min; the reaction time is 60-90min; the drying temperature was 70℃and the drying time was 12 hours.
4. Use of a chlorine-doped cuprous oxide/polyaniline/ITO photocatalytic film as claimed in any one of claims 1-3 for degrading organic pollutants of water bodies.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2138608A1 (en) * | 2008-06-24 | 2009-12-30 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Process for preparing a transparent and conductive film on a substrate |
| CN103191738A (en) * | 2013-04-09 | 2013-07-10 | 云南大学 | Glass fiber loading cuprous oxide visible light catalyst and application thereof |
| CN108130552A (en) * | 2017-12-27 | 2018-06-08 | 东莞理工学院 | A kind of polyaniline cuprous oxide composite material and its preparation method and application |
| CN113804738A (en) * | 2021-08-26 | 2021-12-17 | 宁德师范学院 | Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2138608A1 (en) * | 2008-06-24 | 2009-12-30 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Process for preparing a transparent and conductive film on a substrate |
| CN103191738A (en) * | 2013-04-09 | 2013-07-10 | 云南大学 | Glass fiber loading cuprous oxide visible light catalyst and application thereof |
| CN108130552A (en) * | 2017-12-27 | 2018-06-08 | 东莞理工学院 | A kind of polyaniline cuprous oxide composite material and its preparation method and application |
| CN113804738A (en) * | 2021-08-26 | 2021-12-17 | 宁德师范学院 | Polyaniline-loaded cuprous oxide sensing electrode and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| Cu_2O/聚苯胺/不锈钢电极光电催化还原CO_2;张芹;梁燕萍;;精细化工(第11期);第43-47页 * |
| Electrodeposition of mesoporous bilayers of polyaniline supported Cu2O semiconductor films from lyotropic liquid crystalline phase;Tong Xue等;Chemical Engineeering Science(第80期);452-459 * |
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