CN113399002A - Photocatalytic nanofiber membrane for dye degradation and preparation method thereof - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 230000015556 catabolic process Effects 0.000 title claims abstract description 31
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 80
- 229920000767 polyaniline Polymers 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004246 zinc acetate Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 44
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims 2
- 238000001308 synthesis method Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000013557 residual solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
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- 238000012512 characterization method Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 54
- 239000000975 dye Substances 0.000 description 28
- 239000011787 zinc oxide Substances 0.000 description 27
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 13
- 229940012189 methyl orange Drugs 0.000 description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- 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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Abstract
The invention discloses a photocatalytic nanofiber membrane for dye degradation and a preparation method thereof. The film can realize high-efficiency dye degradation under the illumination condition, and the organic dye is completely degraded in a photocatalytic manner after illumination for 90 min. The preparation method of the membrane is also simple, Polyacrylonitrile (PAN) is dissolved in N, N-Dimethylformamide (DMF) to obtain a spinning solution, a gas-assisted method is adopted to prepare the PAN nanofiber membrane, the PANI/PAN nanofiber membrane is prepared after polyaniline modification, the PANI/PAN nanofiber membrane is alternately dipped and coated by a zinc acetate solution and a sodium hydroxide solution, and the PANI/PAN nanofiber membrane and Zn (NO) which are alternately dipped and coated are mixed3)2·6H2O and C6H12N4And carrying out hydrothermal reaction on the prepared hydrothermal reaction precursor solution. The characterization of various test means on the material shows the modification effectThe method is good, and can verify the efficacy of the photocatalytic nanofiber membrane with the dye degradation performance.
Description
Technical Field
The invention relates to the technical field of preparation of dye degradation films, and discloses a high-efficiency composite nanofiber film for preparing photocatalytic degradation organic dyes, which normally works under the irradiation of visible light.
Background
In recent years, the preparation of dye degradation materials has become an urgent task because water pollution caused by wastewater containing organic dyes seriously harms human life health due to the continuous occurrence of serious wastewater pollution events on a global scale. In the past decades, researchers have adopted many new methods to degrade organic dyes, but these methods generally have the disadvantages of low degradation efficiency, complicated operation process, high equipment cost, secondary pollution and the like, and the disadvantages severely limit the practical application of the methods. At present, the membrane degradation technology is an effective method for treating wastewater containing organic dyes, and has attracted extensive attention of researchers because of the advantages of high degradation efficiency, environmental friendliness, simple and reliable operation and the like.
The photocatalysis can induce the electron transfer of the semiconductor photocatalyst to generate hydroxyl free radicals, and the hydroxyl free radicals react with the organic dye. A series of metal oxides, sulfides and composite metal oxides with good photocatalytic activity and stability have been successfully applied to the degradation of organic dyes in recent years.
The nanofiber membrane has the characteristics of porous structure, large specific surface area, strong permeability and controllability, and is widely concerned in the field of dye degradation. The photocatalytic active substance loaded on the surface of the nanofiber membrane is the key of dye degradation. Due to the fact that the photocatalysis active substance is loaded, the nanofiber membrane has high degradation efficiency on organic dye, and becomes a research hotspot in the field of preparation of dye degradation membranes in recent years. However, the currently reported membrane materials still have the problems of poor dye degradation efficiency, easy pollution, poor tolerance, low environmental protection and the like, and the practical application of the membrane materials is seriously hindered. Therefore, the development of a low-cost and simple method for preparing the dye degradation fiber membrane with high degradation efficiency, strong environmental protection and good stability is imminent for the degradation of the dye in the wastewater pollutants.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the photocatalytic nanofiber membrane for dye degradation and the preparation method thereof, which effectively improve the dye degradation performance of the fiber membrane and have the feasibility of industrial production.
In order to solve the technical problems, the invention provides the following technical scheme: a photocatalysis nanofiber membrane for dye degradation and a preparation method thereof comprise the following steps:
polyacrylonitrile (PAN) was dissolved in N, N-Dimethylformamide (DMF) to obtain a PAN solution. Preparing PAN into a nanofiber membrane by adopting gas spinning for 1h through a gas-assisted method, modifying the PAN membrane by using an aniline solution and an ammonium persulfate solution, and polymerizing for 2h in a nitrogen atmosphere to obtain the PANI/PAN membrane. And then, alternately dip-coating the membrane in a zinc acetate solution and a sodium hydroxide solution for multiple times to obtain the initially modified PANI/PAN membrane. And finally, loading ZnO on the surface of the PANI/PAN film by using a hydrothermal method to obtain the ZnO/PANI/PAN photocatalytic composite nanofiber film for dye degradation.
In the step, the concentration of the PAN solution is 0.015 mol/L.
The concentration of the aniline solution is 0.01mol/L, and the concentration of the ammonium persulfate solution is 0.02 mol/L.
The concentration of the zinc acetate solution is 15mg/mL, and the concentration of the sodium hydroxide solution is 0.1 mol/L.
The number of alternate dip-coating times was 5.
The gas-assisted spinning conditions are as follows: the injection speed of the needle head under the action of the propulsion pump is 2.5mL/h, and the applied airflow is maintained at 8L/min. The horizontal distance between the needle and the collector was kept at 15 cm.
Compared with the prior art, the invention has the following remarkable advantages:
compared with the prior art, the invention introduces the zinc oxide nano-particles with photocatalytic activity to obtain the nano-fiber membrane with dye degradation effect on the premise of not influencing other properties of the nano-fiber membrane. The zinc oxide nano particles loaded on the surface of the film improve the degradation performance of the dye, the degradation efficiency of the film is improved, and the film can be recycled after verification.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without any creative effort. Wherein:
FIG. 1 is a schematic diagram of a ZnO/PANI/PAN composite nanofiber membrane photocatalytic mechanism.
FIG. 2 is a diagram of the surface morphology and elemental composition of a fiber membrane. (a) SEM image of raw PAN fiber membrane. (b) SEM images of PANI/PAN fibrous membranes. (c) SEM image of ZnO/PANI/PAN fiber membrane. (d) SEM-EDS spectrum of ZnO/PANI/PAN membrane.
FIG. 3 is a spectrum diagram of absorption peaks of a ZnO/PANI/PAN film on a Methyl Orange (MO) aqueous solution under different illumination times.
FIG. 4 is a digital photograph and an absorption peak spectrum of the MO aqueous solution change with time for the ZnO/PANI/PAN film.
FIG. 5 is a graph of the photocatalytic degradation rate of PAN, PANI/PAN, ZnO/PAN, and ZnO/PANI/PAN films in aqueous MO solutions under light conditions.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments of the present invention are described in detail below with reference to examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and similarly generalized by those of skill in the art without departing from the spirit of the present invention and therefore is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Adding 0.02mol of PAN and 0.02mol of DMF into a dry four-mouth flask (mainly comprising a magnetic stirrer and a thermometer), fully mixing, and stirring for 8-10 h at room temperature by using the magnetic stirrer to obtain a uniform PAN spinning solution with the concentration of 0.015 mol/L. In the assembled spinning system, the spinning was carried out at a needle injection speed of 2.5mL/h, the applied air flow was maintained at 8L/min, and the horizontal distance between the needle and the collector was maintained at 15 cm. After the PAN fiber membrane prepared by air spinning was peeled off from the collector, it was dried in a vacuum oven at 90 ℃ for 5 hours to completely remove the small molecular weight residues (including water, organic solvent) on the surface.
Example 2
(1) mu.L of aniline monomer was dissolved in 40mL hydrochloric acid (1mol/L) by pipetting with a pipette gun, and after stirring sufficiently, a 4 wt% aniline solution was obtained.
(2) 0.1g of ammonium persulfate is accurately weighed and dissolved in 40mL of hydrochloric acid (1mol/L), and the solution is fully stirred to obtain 6 wt% of ammonium persulfate solution.
(3) The PAN membrane (2cm multiplied by 2cm) is immersed in the aniline solution, and the ammonium persulfate solution is slowly dropped into the aniline solution containing the PAN nanofiber membrane. After 2h of polymerization in a nitrogen atmosphere, a dark green PANI/PAN nanofiber membrane was obtained. Finally, the membrane is washed by deionized water and then is placed in a vacuum oven to be dried for 2 hours at the temperature of 70 ℃.
(4) The PANI/PAN nanofiber membrane was immersed in a zinc acetate solution for 2min and then heat treated in a vacuum oven at 125 ℃ for 10 min. And then soaking the dried PANI/PAN membrane in 1mol/L NaOH aqueous solution for 2min, then carrying out heat treatment at 125 ℃ for 10min, and repeating the step for 5 times to ensure that ZnO seed crystals are uniformly loaded on the surface of the PANI/PAN nanofiber membrane.
(5) Accurately weighing 3.0g C6H12N4And 1.5g Zn (NO)3)2·6H2And O, adding 100mL of deionized water to dissolve to obtain hydrothermal reaction precursor liquid.
(6) And (3) placing the PANI/PAN nanofiber membrane with the surface loaded with the ZnO seeds and the hydrothermal reaction precursor solution into a hydrothermal reaction kettle, reacting for 8 hours at 90 ℃, and then washing for many times by using deionized water and ethanol. Finally, the photocatalytic ZnO/PANI/PAN composite nanofiber membrane for dye degradation is obtained, and the photocatalytic mechanism of the photocatalytic ZnO/PANI/PAN composite nanofiber membrane is shown in figure 1.
Example 3
The surface morphology of the PAN film, PANI/PAN film, ZnO/PANI/PAN film prepared in example 2 was observed under vacuum conditions at an acceleration voltage of 20kV using a field emission scanning electron microscope (JSM-7600F, japan). Continuous gaps can be clearly observed among fibers on the PAN film, smooth PAN nanofibers become rough after being wrapped by a polyaniline coating, and needle-shaped nano ZnO grows on the surfaces of the PAN nanofibers after hydrothermal treatment. The field emission scanning electron microscope used in this time has the function of analyzing elements, and the elements on the surface of the film are confirmed through EDS analysis, so that the success of film modification is proved, as shown in FIG. 2.
Example 4
The organic dye in the solution was quantitatively analyzed using a full-wavelength light-absorbing microplate reader (ReadMax-1900, Shanghai Flash spectral Technology CO., China). On the basis, the PAN film, the PANI/PAN film, the ZnO/PAN film and the ZnO/PANI/PAN film are tested for the photocatalytic degradation performance of the organic dye.
By taking the organic dye MO as an example, a photocatalytic degradation experiment is carried out, and the photocatalytic degradation performance of the PAN film, the PANI/PAN film, the ZnO/PAN film and the ZnO/PANI/PAN film on the MO-containing solution is examined. As shown in FIG. 3 and FIG. 4, the absorption spectra of the MO solution (ZnO/PANI/PAN film is present) irradiated by the photocatalytic xenon lamp at different times show that the ZnO/PANI/PAN film has good photocatalytic degradation capability. With the continuous degradation of the ZnO/PANI/PAN film surface catalyst, the MO solution gradually changes from orange to colorless and transparent, and the characteristic peak of the absorbance of MO at 469nm gradually weakens almost to zero after the MO solution is irradiated for 90 min. For MO dye solution of PAN film or ZnO/PAN film, the characteristic peak intensity of MO aqueous solution is almost unchanged, and ZnO/PAN film has certain photocatalytic degradation effect on MO, but the degradation effect is not as good as that of ZnO/PANI/PAN film (figure 5).
The present invention provides a photocatalytic nanofiber membrane for dye degradation and a method for preparing the same, and a method and a way for implementing the technical scheme are numerous, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several improvements and decorations can be made without departing from the principle of the present invention, and these improvements and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the embodiment can be realized by the prior art.
Claims (7)
1. A photocatalysis nanofiber membrane for dye degradation and a preparation method thereof are characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
polyacrylonitrile (PAN) monomer is dissolved in N, N-Dimethylformamide (DMF) to prepare PAN solution, and the PAN solution is prepared into a PAN membrane by a gas-assisted spinning method.
The PANI/PAN membrane is obtained by modifying the PAN membrane by adopting a polyaniline in-situ synthesis method.
And (3) alternately dip-coating the modified PANI/PAN membrane by adopting a zinc acetate solution and a NaOH solution.
The photocatalytic nanofiber membrane is obtained by carrying out hydrothermal reaction on a hydrothermal reaction precursor solution and a dipped PANI/PAN membrane and a preparation method thereof.
2. The photocatalytic nanofiber membrane as claimed in claim 1 and the preparation method thereof, wherein the PAN solution is made into PAN nanofiber membrane by gas-assisted spinning method, which comprises, after gas spinning for 1h, obtaining PAN nanofiber membrane, then peeling the fiber membrane from the collector, and drying in a vacuum oven at 90 ℃ for 5h to remove residual solvent, the ambient temperature and humidity of the whole gas spinning process are respectively kept at 25 ± 5 ℃ and 40 ± 5%, wherein the gas-assisted spinning conditions comprise: the injection speed of the needle head under the action of the propulsion pump is 2.5mL/h, and the applied airflow is maintained at 8L/min. The horizontal distance between the needle and the collector was kept at 15 cm.
3. The photocatalytic nanofiber membrane as claimed in claim 1, and the preparation method thereof, wherein the preparation of PANI/PAN membrane by in-situ synthesis method comprises immersing the PAN membrane in polyaniline solution. And slowly dropping the ammonium persulfate/hydrochloric acid solution into the aniline solution containing the PAN nanofiber membrane. After 2h of polymerization in nitrogen atmosphere, the residual impurities on the membrane were removed with deionized water and dried in a vacuum oven at 70 ℃ for 2 h.
4. The photocatalytic nanofiber membrane as claimed in claim 1, and the preparation method thereof, wherein the preparation of the ZnO/PANI/PAN membrane by the alternate dip coating method comprises immersing the PANI/PAN membrane in a zinc acetate solution for 2min, and then heat-treating the PANI/PAN membrane in a vacuum oven at 125 ℃ for 10 min. Then soaking the dried PANI/PAN membrane in NaOH solution for 2min, then carrying out heat treatment at 125 ℃ for 10min, and repeating the steps for 3 times. And then mixing the dipped PANI/PAN membrane and the hydrothermal reaction precursor solution, adding the mixture into a polytetrafluoroethylene reaction kettle, reacting for 8 hours at 90 ℃ by a hydrothermal method, and washing for many times by deionized water and ethanol.
5. The photocatalytic nanofiber membrane as claimed in claim 1, wherein the zinc acetate solution is prepared by dissolving zinc acetate in deionized water and stirring the solution at room temperature.
6. The photocatalytic nanofiber membrane as claimed in claim 1, wherein the NaOH solution is prepared by dissolving NaOH in deionized water and stirring the solution at room temperature.
7. The photocatalytic nanofiber membrane as claimed in any one of claims 1 to 6, and the nanofiber membrane prepared by the preparation method thereof, wherein the photocatalytic nanofiber membrane is characterized in that: the organic dye in the solution can be continuously degraded under the irradiation of visible light until the organic dye is completely degraded.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155644A (en) * | 2022-08-02 | 2022-10-11 | 西北师范大学 | Increase g-C 3 N 4 Method for catalytic activation of photocatalytic fiber membrane |
| CN115212880A (en) * | 2021-12-29 | 2022-10-21 | 昆明理工大学 | Preparation method of Cu @ g-PAN + PANI/STO photocatalyst |
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2021
- 2021-05-31 CN CN202110605838.3A patent/CN113399002A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115212880A (en) * | 2021-12-29 | 2022-10-21 | 昆明理工大学 | Preparation method of Cu @ g-PAN + PANI/STO photocatalyst |
| CN115155644A (en) * | 2022-08-02 | 2022-10-11 | 西北师范大学 | Increase g-C 3 N 4 Method for catalytic activation of photocatalytic fiber membrane |
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