CN117599834B - Photocatalytic nanofiber membrane and preparation method and application thereof - Google Patents
Photocatalytic nanofiber membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN117599834B CN117599834B CN202410089886.5A CN202410089886A CN117599834B CN 117599834 B CN117599834 B CN 117599834B CN 202410089886 A CN202410089886 A CN 202410089886A CN 117599834 B CN117599834 B CN 117599834B
- Authority
- CN
- China
- Prior art keywords
- photocatalytic
- temperature
- electrostatic spinning
- reaction system
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 109
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 239000002121 nanofiber Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 53
- 238000009987 spinning Methods 0.000 claims abstract description 43
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000007146 photocatalysis Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 15
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 15
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 15
- 229940072172 tetracycline antibiotic Drugs 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000011159 matrix material Substances 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 16
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 230000001276 controlling effect Effects 0.000 description 18
- 239000000835 fiber Substances 0.000 description 13
- 239000004098 Tetracycline Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 235000019364 tetracycline Nutrition 0.000 description 10
- 150000003522 tetracyclines Chemical class 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 229960002180 tetracycline Drugs 0.000 description 8
- 229930101283 tetracycline Natural products 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
-
- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
-
- 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
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalysis nanofiber membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing electrostatic spinning precursor liquid by using a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material; preparing a nano Fe 3O4 reaction system by using anhydrous ferric trichloride, diethylene glycol solution, trisodium citrate and the like; immersing half of the volume of a spinning roller in a nano Fe 3O4 reaction system, carrying out electrostatic spinning by using an electrostatic spinning precursor liquid, and controlling the nano fiber to sequentially pass through a first temperature region and a second temperature region with the temperature higher than that of the first temperature region to obtain the photocatalysis nano fiber film. The photocatalysis nanofiber membrane provided by the invention can adsorb tetracycline antibiotic pollutants on the surface and inside the holes of the membrane material for catalytic degradation, improves the tetracycline antibiotic treatment efficiency, has strong pollution resistance, and prolongs the desorption period and the service period of the membrane material.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a photocatalytic nanofiber membrane and a preparation method and application thereof.
Background
In recent years, various new types of contaminants have emerged, of which antibiotic-type contaminants typified by tetracyclines are the most typical. Antibiotics have been widely used in clinical medicine and aquaculture for livestock and poultry since their spontaneous emission, however antibiotics present some potential ecological safety risks while treating and preventing bacterial infections.
At present, in a plurality of treatment methods such as a membrane separation method, an ozone oxidation method and the like, the photocatalytic oxidation technology is widely researched due to the advantages of high efficiency, mild and stable reaction conditions, greenness, no pollution and the like. However, the existing photocatalytic materials have some defects in practical use: 1) The photo-generated electrons and holes of the traditional photo-catalytic material are difficult to separate, so that the photo-generated electrons and the holes are easy to combine in the reaction process, and the photo-catalytic efficiency is greatly affected; 2) The photocatalytic material is granular and easy to run off, is difficult to uniformly and fully contact with pollutants, and has low repetition rate or can not be repeatedly used in batches in practical application.
Under the foregoing conditions, photocatalytic film materials have grown, and more scholars have tried to combine photocatalytic materials with film materials, there are generally two ways of combining: firstly, fusing the photocatalytic material in the process of preparing the flat membrane, and secondly, loading the photocatalytic material on the surface of the membrane after membrane preparation. The first method has the defects that most of the photocatalytic material is coated in the film body, the photocatalytic material cannot be covered when the photocatalytic material is irradiated by visible light, material waste and efficiency reduction are caused, and a film structure (the photocatalytic material catalyzes the film structure) can be damaged after long-time use; the second method has the defects that the material utilization rate is low when the material is loaded on the surface of the membrane, and the physical loading mode causes insufficient binding force of the photocatalytic material and is easy to break away from the surface of the membrane material to cause loss; in addition, the film material has the problems of low strength, poor elastoplasticity and the like. The traditional preparation process of the photocatalytic material can not meet the requirements of the actual treatment process, and also greatly limits the application of the photocatalytic material in the field of tetracycline antibiotic degradation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a photocatalysis nanofiber membrane, a preparation method and application thereof, and the photocatalysis nanofiber membrane is used for adsorbing tetracycline antibiotic pollutants on the surface of a membrane material and in holes for catalytic degradation, so that the treatment efficiency of the tetracycline antibiotic is improved, and the photocatalysis nanofiber membrane is strong in pollution resistance, and the desorption period and the service period of the membrane material are obviously prolonged.
The invention provides the following technical scheme:
In a first aspect, a method for preparing a photocatalytic nanofiber membrane is provided, comprising the steps of:
calcining urea to obtain g-C 3N4, placing g-C 3N4 in ethanol for ultrasonic dispersion, adding nickel nitrate hexahydrate and urea, stirring, and repeatedly calcining to obtain a 10 nm-level p-n heterojunction flower-shaped g-C 3N4/NiO photocatalytic material;
Dissolving chitosan and polyvinylpyrrolidone in acetic acid solution, stirring to obtain a spinning matrix, adding the g-C 3N4/NiO photocatalytic material into the spinning matrix, and uniformly dispersing to obtain an electrostatic spinning precursor solution;
Adding anhydrous ferric trichloride into a diethylene glycol solution, uniformly stirring to obtain a preliminary reaction system, and adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system to obtain a nano Fe 3O4 reaction system;
And (3) transferring the electrostatic spinning precursor liquid into an electrostatic spinning machine injector, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system, and controlling the spun nano fiber to sequentially pass through a first temperature region and a second temperature region with the temperature higher than that of the first temperature region for electrostatic spinning to obtain the photocatalysis nano fiber film.
Further, the heating speed of urea calcination is 15-20 ℃/min, and the urea is heated to 600-650 ℃ and calcined for 4-5 hours.
Further, the mass ratio of the g-C 3N4 to the ethanol, the nickel nitrate hexahydrate and the urea is 1 (20-40): 1-5.
Further, the method for repeating calcination includes: heating to 150 ℃ at a speed of 5 ℃/min for calcination for 4 hours, heating to 450 ℃ at a speed of 10-20 ℃/min for calcination for 4 hours, cooling, and circulating for three times.
Further, the mass ratio of the chitosan to the polyvinylpyrrolidone to the acetic acid is 1 (0.05-0.15) (50-100); the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material is (8-15): 1.
Further, the mass ratio of the anhydrous ferric trichloride to the diglycol is 1 (70-90); the mass ratio of the primary reaction system to the ethanol to the trisodium citrate to the anhydrous sodium acetate is 80 (1-3), and the mass ratio of the primary reaction system to the ethanol to the anhydrous sodium acetate is 1-5, and the mass ratio of the primary reaction system to the ethanol to the anhydrous sodium acetate is 1-3.
Further, the voltage of the electrostatic spinning is 18-20 KV, the aperture of a nozzle of an electrostatic spinning machine injector is 1.0-2.0 mm, the flow rate of a solution is 1.0-2.0 mL/h, the speed of a spinning roller is 5-80 r/min, and the receiving time is 10-400 min.
Further, the temperature of the first temperature zone is 25-30 ℃, and the height is 30-50 cm; the temperature of the second temperature zone is 70-80 ℃, and the height of the second temperature zone is 20-40 cm.
In a second aspect, there is provided a photocatalytic nanofiber membrane prepared by the method of the first aspect.
In a third aspect, the application of the photocatalytic nanofiber membrane in the second aspect in synchronous adsorption and degradation of tetracycline antibiotics is provided.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material is prepared, the separation efficiency of photo-generated electrons and holes is improved through the physical structure and the heterojunction structure, and the photocatalytic efficiency is improved, and the size and the surface morphology of the material are controlled, so that the material can uniformly cover the fiber surface; then Chitosan (CS) is used as a matrix, polyvinylpyrrolidone (PVP) is used as a pore-forming agent, the spinnability of the electrostatic spinning precursor liquid is improved, CS can be used as an adsorbent for chemisorption of tetracycline antibiotic pollutants, and index parameters such as nanofiber strength, elastoplasticity and the like are improved by controlling spinning parameters and conditions of a first temperature zone and a second temperature zone in the electrostatic spinning process; finally, collecting the spun nanofiber on a spinning roller with half volume immersed in a nano Fe 3O4 reaction system, realizing film making and hole forming at the same time, further improving adsorption capacity and fiber film strength performance indexes, obtaining mesoporous morphology on the fiber surface so that pollutants can react on the fiber surface and inside, and improving residence reaction time;
(2) The photocatalysis nanofiber membrane prepared by the invention has larger specific surface area, membrane strength and other physical properties, can be applied to the application scene of slow membrane filtration, and can solve the problem of secondary pollution caused by material loss;
(3) The photocatalysis nanofiber membrane prepared by the invention fully utilizes the adsorption capacity of CS matrix and supported nano Fe 3O4 particles and has a mesoporous structure, can provide enough physical and chemical adsorption capacity, adsorbs tetracycline antibiotic pollutants to the surface of a membrane material and the inside of a hole for catalytic degradation, and solves the problem of insufficient adsorption capacity of the traditional membrane material on the pollutants; in addition, the photocatalytic nanofiber membrane prepared by the invention has the advantages that the anti-pollution capability is improved due to the tetracycline pollution layer attached to the photocatalytic degradation surface, and the desorption period and the service period of the membrane material are obviously prolonged.
Drawings
FIG. 1 is a schematic view of a process for preparing a photocatalytic nanofiber membrane according to an embodiment of the present invention;
FIG. 2 is an SEM image of a g-C 3N4/NiO photocatalytic material prepared according to example 5 of the present invention;
FIG. 3 is an SEM image of a photocatalytic nanofiber membrane prepared according to example 5 of the present invention;
FIG. 4 is an XRD comparison of g-C 3N4/NiO prepared in example 5 of the present invention with a single catalyst;
FIG. 5 is an XPS chart of the photocatalytic nanofiber membrane prepared in example 5 of the present invention;
FIG. 6 is a graph showing the comparison of the properties of the photocatalytic nanofiber membranes prepared in example 5 and comparative examples 1-3 according to the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
As shown in fig. 1, the present embodiment provides a preparation method of a photocatalytic nanofiber membrane, which specifically includes the following steps:
Step 1, preparing a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material.
Urea was warmed up at a rate of 15 ℃/min, the temperature after warming up was controlled to 600 ℃, and calcined at this temperature for 4 hours, to obtain g-C 3N4 powder.
Putting the prepared g-C 3N4 into ethanol, performing ultrasonic dispersion for 30min, adding nickel nitrate hexahydrate and urea, performing magnetic stirring for 30min, calcining for 4h at a low temperature of 150 ℃ (the heating rate is 5 ℃/min), calcining for 4h at a high temperature of 450 ℃ (the heating rate is 10 ℃/min), and performing circulation for three times in a low-temperature and high-temperature process, so as to finally obtain the 10 nm-grade p-n heterojunction flower-spherical g-C 3N4/NiO photocatalytic material.
And 2, preparing an electrostatic spinning precursor solution.
And (3) dissolving CS and PVP powder in an acetic acid solution according to the mass ratio of CS to PVP to acetic acid of 1:0.05:50, and magnetically stirring for 12 hours at room temperature to prepare the spinning matrix.
Slowly adding the g-C 3N4/NiO photocatalytic material prepared in the step 1 into the spinning matrix according to the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material of 8:1, continuing magnetic stirring for 12 hours, and then carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the solution, thereby obtaining the electrostatic spinning precursor solution.
And 3, preparing a nano Fe 3O4 reaction system.
Adding anhydrous ferric trichloride into diethylene glycol solution according to the mass ratio of the anhydrous ferric trichloride to the diethylene glycol of 1:70, controlling the reaction temperature to be 80 ℃, and magnetically stirring until the solution is uniform, thus obtaining a primary reaction system.
Adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system according to the mass ratio of the preliminary reaction system to the ethanol, the trisodium citrate and the anhydrous sodium acetate of 80:1:1, maintaining the water bath temperature at 80 ℃, and magnetically stirring for 1h to obtain the nano Fe 3O4 reaction system.
And 4, preparing the photocatalysis nanofiber membrane by electrostatic spinning.
Moving an electrostatic spinning precursor into an electrostatic spinning machine injector, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system kept at 80 ℃, controlling the electrostatic spinning voltage to be 18KV, and controlling the aperture of a nozzle of the electrostatic spinning machine injector to be 1.0-2.0 mm and the flow rate of a solution to be 1.0mL/h; controlling the spun nanofiber to sequentially pass through a first temperature zone and a second temperature zone, wherein the temperature of the first temperature zone (low temperature zone) is 25 ℃, the height is 30cm, the temperature of the second temperature zone (high temperature zone) is 70 ℃, and the height is 20cm; the speed of the spinning roller is regulated to be 5r/min, and the receiving time is regulated to be 10min; and carrying out electrostatic spinning, collecting and obtaining photocatalysis nano fibers on a spinning roller, and drying to obtain the photocatalysis nano fiber film loaded with nano Fe 3O4 particles.
Example 2
The embodiment provides a preparation method of a photocatalysis nanofiber membrane, which comprises the following specific steps:
Step 1, preparing a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material.
Urea was warmed up at a rate of 20 ℃/min, the temperature after warming up was controlled to 650 ℃, and calcined at this temperature for 5 hours, to obtain g-C 3N4 powder.
Putting the prepared g-C 3N4 into ethanol, carrying out ultrasonic dispersion for 30min, adding nickel nitrate hexahydrate and urea, wherein the mass ratio of the g-C 3N4 to the ethanol, the nickel nitrate hexahydrate and the urea is 1:5:5, magnetically stirring for 30min, calcining for 4h at a low temperature of 150 ℃ (the heating rate is 5 ℃/min), calcining for 4h at a high temperature of 450 ℃ (the heating rate is 15 ℃/min), and circulating for three times in a low-temperature and high-temperature process to finally obtain the 10 nm-grade p-n heterojunction flower-spherical g-C 3N4/NiO photocatalytic material.
And 2, preparing an electrostatic spinning precursor solution.
The CS and PVP powder is dissolved in acetic acid solution according to the mass ratio of CS to PVP to acetic acid of 1:0.15:100, and magnetically stirred for 12 hours at room temperature to prepare the spinning matrix.
Slowly adding the g-C 3N4/NiO photocatalytic material prepared in the step 1 into the spinning matrix according to the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material of 15:1, continuing magnetic stirring for 12 hours, and then carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the solution, thereby obtaining the electrostatic spinning precursor solution.
And 3, preparing a nano Fe 3O4 reaction system.
Adding anhydrous ferric trichloride into diethylene glycol solution according to the mass ratio of the anhydrous ferric trichloride to the diethylene glycol of 1:90, controlling the reaction temperature to be 80 ℃, and magnetically stirring until the solution is uniform, thus obtaining a primary reaction system.
Adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system according to the mass ratio of the preliminary reaction system to the ethanol, the trisodium citrate and the anhydrous sodium acetate of 80:3:5:3, maintaining the water bath temperature at 80 ℃, and magnetically stirring for 1h to obtain the nano Fe 3O4 reaction system.
And 4, preparing the photocatalysis nanofiber membrane by electrostatic spinning.
Moving an electrostatic spinning precursor into an injector of an electrostatic spinning machine, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system maintained at 80 ℃, and controlling the electrostatic spinning voltage to be 20KV, wherein the aperture of a nozzle is 2.0mm, and the flow rate of a solution is 2.0mL/h; controlling the spun nanofiber to sequentially pass through a first temperature zone and a second temperature zone, wherein the temperature of the first temperature zone (low temperature zone) is 30 ℃, the height is 50cm, the temperature of the second temperature zone (high temperature zone) is 80 ℃, and the height is 40cm; the speed of the spinning roller is regulated to 80r/min, and the receiving time is 400min; and carrying out electrostatic spinning, collecting and obtaining photocatalysis nano fibers on a spinning roller, and drying to obtain the photocatalysis nano fiber film loaded with nano Fe 3O4 particles.
Example 3
The embodiment provides a preparation method of a photocatalysis nanofiber membrane, which comprises the following specific steps:
Step 1, preparing a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material.
Urea was heated at a rate of 20 ℃/min, the temperature after the heating was controlled to 640 ℃, and calcined at this temperature for 5 hours, to obtain g-C 3N4 powder.
Putting the prepared g-C 3N4 into ethanol, performing ultrasonic dispersion for 30min, adding nickel nitrate hexahydrate and urea, performing magnetic stirring for 30min, calcining for 4h at a low temperature of 150 ℃ (the heating rate is 5 ℃/min), calcining for 4h at a high temperature of 450 ℃ (the heating rate is 20 ℃/min), and performing circulation for three times in a low-temperature and high-temperature process, so as to finally obtain the 10 nm-grade p-n heterojunction flower-spherical g-C 3N4/NiO photocatalytic material.
And 2, preparing an electrostatic spinning precursor solution.
And (3) dissolving CS and PVP powder in an acetic acid solution according to the mass ratio of CS to PVP to acetic acid of 1:0.07:60, and magnetically stirring for 12 hours at room temperature to prepare the spinning matrix.
Slowly adding the g-C 3N4/NiO photocatalytic material prepared in the step 1 into the spinning matrix according to the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material of 10:1, continuing magnetic stirring for 12 hours, and then carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the solution, thereby obtaining the electrostatic spinning precursor solution.
And 3, preparing a nano Fe 3O4 reaction system.
Adding anhydrous ferric trichloride into diethylene glycol solution according to the mass ratio of the anhydrous ferric trichloride to the diethylene glycol of 1:75, controlling the reaction temperature to be 80 ℃, and magnetically stirring until the solution is uniform, thus obtaining a primary reaction system.
Adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system according to the mass ratio of the preliminary reaction system to the ethanol, trisodium citrate and anhydrous sodium acetate of 80:2:2, maintaining the water bath temperature at 80 ℃, and magnetically stirring for 1h to obtain the nano Fe 3O4 reaction system.
And 4, preparing the photocatalysis nanofiber membrane by electrostatic spinning.
Moving an electrostatic spinning precursor into an injector of an electrostatic spinning machine, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system maintained at 80 ℃, and controlling the electrostatic spinning voltage to be 19KV, wherein the aperture of a nozzle is 1.3mm, and the flow rate of a solution is 1.2mL/h; controlling the spun nanofiber to sequentially pass through a first temperature zone and a second temperature zone, wherein the temperature of the first temperature zone (low temperature zone) is 28 ℃, the height is 40cm, the temperature of the second temperature zone (high temperature zone) is 75 ℃, and the height is 30cm; the speed of the spinning roller is regulated to be 30r/min, and the receiving time is regulated to be 50min; and carrying out electrostatic spinning, collecting and obtaining photocatalysis nano fibers on a spinning roller, and drying to obtain the photocatalysis nano fiber film loaded with nano Fe 3O4 particles.
Example 4
The embodiment provides a preparation method of a photocatalysis nanofiber membrane, which comprises the following specific steps:
Step 1, preparing a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material.
The urea is heated at a speed of 20 ℃/min, the temperature after the temperature rising is controlled to 650 ℃, and the urea is calcined for 4 hours at the temperature, so as to obtain g-C 3N4 powder.
Putting the prepared g-C 3N4 into ethanol, performing ultrasonic dispersion for 30min, adding nickel nitrate hexahydrate and urea, performing magnetic stirring for 30min, calcining for 4h at a low temperature of 150 ℃ (the heating rate is 5 ℃/min), calcining for 4h at a high temperature of 450 ℃ (the heating rate is 15 ℃/min), and performing circulation for three times in a low-temperature and high-temperature process, so as to finally obtain the 10 nm-grade p-n heterojunction flower-spherical g-C 3N4/NiO photocatalytic material.
And 2, preparing an electrostatic spinning precursor solution.
And (3) dissolving CS and PVP powder in an acetic acid solution according to the mass ratio of CS to PVP to acetic acid of 1:0.1:60, and magnetically stirring for 12 hours at room temperature to prepare the spinning matrix.
Slowly adding the g-C 3N4/NiO photocatalytic material prepared in the step 1 into the spinning matrix according to the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material of 10:1, continuing magnetic stirring for 12 hours, and then carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the solution, thereby obtaining the electrostatic spinning precursor solution.
And 3, preparing a nano Fe 3O4 reaction system.
Adding anhydrous ferric trichloride into diethylene glycol solution according to the mass ratio of the anhydrous ferric trichloride to the diethylene glycol of 1:80, controlling the reaction temperature to be 80 ℃, and magnetically stirring until the solution is uniform, thus obtaining a primary reaction system.
Adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system according to the mass ratio of the preliminary reaction system to the ethanol, the trisodium citrate and the anhydrous sodium acetate of 80:2:1:1, maintaining the water bath temperature at 80 ℃, and magnetically stirring for 1h to obtain the nano Fe 3O4 reaction system.
And 4, preparing the photocatalysis nanofiber membrane by electrostatic spinning.
Moving an electrostatic spinning precursor into an injector of an electrostatic spinning machine, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system maintained at 80 ℃, and controlling the electrostatic spinning voltage to be 20KV, wherein the aperture of a nozzle is 1.5mm, and the flow rate of a solution is 1.5mL/h; controlling the spun nanofiber to sequentially pass through a first temperature zone and a second temperature zone, wherein the temperature of the first temperature zone (low temperature zone) is 30 ℃, the height is 50cm, the temperature of the second temperature zone (high temperature zone) is 70 ℃, and the height is 40cm; the speed of the spinning roller is regulated to be 30r/min, and the receiving time is regulated to be 60min; and carrying out electrostatic spinning, collecting and obtaining photocatalysis nano fibers on a spinning roller, and drying to obtain the photocatalysis nano fiber film loaded with nano Fe 3O4 particles.
Example 5
The embodiment provides a preparation method of a photocatalysis nanofiber membrane, which comprises the following specific steps:
Step 1, preparing a 10 nm-level p-n heterojunction flower-ball-shaped g-C 3N4/NiO photocatalytic material.
Urea was warmed up at a rate of 15 ℃/min, the temperature after warming up was controlled to 650 ℃, and calcined at this temperature for 5 hours, to obtain g-C 3N4 powder.
Putting the prepared g-C 3N4 into ethanol, performing ultrasonic dispersion for 30min, adding nickel nitrate hexahydrate and urea, performing magnetic stirring for 30min, calcining for 4h at a low temperature of 150 ℃ (the heating rate is 5 ℃/min), calcining for 4h at a high temperature of 450 ℃ (the heating rate is 15 ℃/min), and performing circulation for three times in a low-temperature and high-temperature process, so as to finally obtain the 10 nm-grade p-n heterojunction flower-spherical g-C 3N4/NiO photocatalytic material.
And 2, preparing an electrostatic spinning precursor solution.
And (3) dissolving CS and PVP powder in an acetic acid solution according to the mass ratio of CS to PVP to acetic acid of 1:0.1:80, and magnetically stirring for 12 hours at room temperature to prepare the spinning matrix.
Slowly adding the g-C 3N4/NiO photocatalytic material prepared in the step 1 into the spinning matrix according to the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material of 10:1, continuing magnetic stirring for 12 hours, and then carrying out ultrasonic treatment on the mixed solution for 2 hours to uniformly disperse the solution, thereby obtaining the electrostatic spinning precursor solution.
And 3, preparing a nano Fe 3O4 reaction system.
Adding anhydrous ferric trichloride into diethylene glycol solution according to the mass ratio of the anhydrous ferric trichloride to the diethylene glycol of 1:80, controlling the reaction temperature to be 80 ℃, and magnetically stirring until the solution is uniform, thus obtaining a primary reaction system.
Adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system according to the mass ratio of the preliminary reaction system to the ethanol, trisodium citrate and anhydrous sodium acetate of 80:3:2:2, maintaining the water bath temperature at 80 ℃, and magnetically stirring for 1h to obtain the nano Fe 3O4 reaction system.
And 4, preparing the photocatalysis nanofiber membrane by electrostatic spinning.
Moving an electrostatic spinning precursor into an injector of an electrostatic spinning machine, immersing half of the volume of a spinning cylinder into a nano Fe 3O4 reaction system maintained at 80 ℃, and controlling the electrostatic spinning voltage to be 20KV, wherein the aperture of a nozzle is 1.5mm, and the flow rate of a solution is 1.5mL/h; controlling the spun nanofiber to sequentially pass through a first temperature zone and a second temperature zone, wherein the temperature of the first temperature zone (low temperature zone) is 25 ℃, the height is 50cm, the temperature of the second temperature zone (high temperature zone) is 80 ℃, and the height is 40cm; the speed of the spinning roller is regulated to be 50r/min, and the receiving time is regulated to be 200min; and carrying out electrostatic spinning, collecting and obtaining photocatalysis nano fibers on a spinning roller, and drying to obtain the photocatalysis nano fiber film loaded with nano Fe 3O4 particles.
Comparative example 1
The difference from example 5 is that: in the step 4, the first temperature zone and the second temperature zone are both low temperature, namely 25 ℃.
Comparative example 2
The difference from example 5 is that: in the step 4, the first temperature zone and the second temperature zone are both high temperature, namely 80 ℃.
Comparative example 3
The difference from example 5 is that: in the step4, the first temperature zone and the second temperature zone adopt a high temperature zone and a low temperature zone respectively, namely, the temperature of the first temperature zone (high temperature zone) is 80 ℃, the height is 40cm, the temperature of the second temperature zone (low temperature zone) is 25 ℃, and the height is 50cm.
Performance characterization example
1. FIGS. 2a and 2b are SEM images of the g-C 3N4/NiO photocatalytic material prepared in step 1 of example 5 at 10nm and 20nm scales, respectively. As can be seen from FIG. 2a, the g-C 3N4/NiO photocatalytic material is in the form of a 10 nm-class p-n heterojunction flower sphere; as can be seen from FIG. 2b, the g-C 3N4/NiO photocatalytic material has uniform nanoparticle size and uniform morphology.
2. Fig. 3a, 3b and 3c are SEM images of the photocatalytic nanofiber membranes prepared in example 5 at scales of 5 μm, 10 μm, and 50 μm, respectively. From the figure, the diameter distribution of the photocatalysis nanofiber membrane is uniform, the surface is smooth and continuous, and the stacking rule is realized.
3. FIG. 4 shows XRD contrast patterns of the g-C 3N4/NiO photocatalytic material prepared in step 1 of example 5 with respect to the single catalyst (NiO and g-C 3N4). The graph shows that the g-C 3N4/NiO photocatalytic material has the characteristic peak position of a single catalyst, and the material is successfully compounded without interference between the composite materials.
4. FIG. 5 is an XPS chart of the photocatalytic nanofiber membrane prepared in example 5. As can be seen from the graph, O, ni, C, N, fe and other characteristic peak positions are obvious, which indicates that the g-C 3N4/NiO photocatalytic material is successfully loaded on the fiber membrane material.
5. Adding 0.2g of the photocatalytic nanofiber membranes prepared in examples 1-5 and comparative examples 1-3 into a membrane filter, filtering 1L of tetracycline sewage with the concentration of 5.0mg/L at the flow rate of 50ml/min, starting a xenon lamp, performing synchronous adsorption and photocatalytic reaction under the ultraviolet-visible light condition, and measuring the removal rate of the first group of tetracyclines after the reaction effect is stable; the tetracycline sewage was continuously treated by the above method, and after ten treatment groups, the stable removal rate of tetracycline in the tenth group was measured, and the results were as shown in table 1 below.
Table 1 Tetracycline removal rates for photocatalytic nanofiber membranes of examples 1-5 and comparative examples 1-3
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| First group of Tetracycline removal (%) | 93.3 | 88.2 | 94.7 | 96.8 | 99.2 | 82.7 | 90.8 | 90.6 |
| Removal of Tetracycline from the tenth group (%) | 91.2 | 71.5 | 89.1 | 92.3 | 96.7 | 71.6 | 86.5 | 85.9 |
As can be seen from Table 1, the material preparation conditions used in example 5 were optimal, and the removal rate and the multiple cycle removal rate of the tetracycline contaminants were both optimal.
6. The photocatalytic nanofiber membranes prepared in example 5 and comparative examples 1 to 3 were subjected to performance test, as shown in fig. 6. FIG. 6a shows the tensile strength performance test results, and it can be seen from the graph that the conditions of the preparation temperature zone of the fiber membrane adopted in example 5 are set to be optimal, and the tensile strength value of the prepared photocatalytic fiber membrane material is highest; FIG. 6b is a graph showing the Young's modulus performance test, wherein the conditions of the fiber membrane preparation temperature zone adopted in example 5 are set to be optimal, and the Young's modulus value of the prepared photocatalytic fiber membrane material is highest; FIG. 6c shows the results of elongation at break performance test, and shows that the conditions of the fiber membrane preparation temperature zone adopted in example 5 are set to be optimal, and the prepared photocatalytic fiber membrane material has the strongest deformability; fig. 6d shows the results of pure water permeability performance test, and it can be seen from the graph that the conditions of the fiber membrane preparation temperature zone adopted in example 5 are set to be optimal, and the prepared photocatalytic fiber membrane material has the maximum filtration flux.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (6)
1. The preparation method of the photocatalysis nanofiber membrane is characterized by comprising the following steps of:
calcining urea to obtain g-C 3N4, placing g-C 3N4 in ethanol for ultrasonic dispersion, adding nickel nitrate hexahydrate and urea, stirring, and repeatedly calcining to obtain a 10 nm-level p-n heterojunction flower-shaped g-C 3N4/NiO photocatalytic material;
Dissolving chitosan and polyvinylpyrrolidone in acetic acid solution, stirring to obtain a spinning matrix, adding the g-C 3N4/NiO photocatalytic material into the spinning matrix, and uniformly dispersing to obtain an electrostatic spinning precursor solution;
Adding anhydrous ferric trichloride into a diethylene glycol solution, uniformly stirring to obtain a preliminary reaction system, and adding ethanol, trisodium citrate and anhydrous sodium acetate into the preliminary reaction system to obtain a nano Fe 3O4 reaction system;
Transferring the electrostatic spinning precursor liquid into an electrostatic spinning machine injector, immersing half of the volume of a spinning roller in a nano Fe 3O4 reaction system, and controlling the spun nano fiber to sequentially pass through a first temperature region and a second temperature region with the temperature higher than that of the first temperature region for electrostatic spinning to obtain a photocatalysis nano fiber film;
The method for repeatedly calcining comprises the following steps: heating to 150 ℃ at a speed of 5 ℃/min for calcination for 4 hours, heating to 450 ℃ at a speed of 10-20 ℃/min for calcination for 4 hours, cooling, and circulating for three times;
The mass ratio of the anhydrous ferric trichloride to the diglycol is 1 (70-90); the mass ratio of the primary reaction system to the ethanol to the trisodium citrate to the anhydrous sodium acetate is 80 (1-3) (1-5) (1-3);
The voltage of the electrostatic spinning is 18-20 KV, the aperture of a nozzle of an injector of an electrostatic spinning machine is 1.0-2.0 mm, the flow rate of a solution is 1.0-2.0 mL/h, the speed of a spinning roller is 5-80 r/min, and the receiving time is 10-400 min;
The temperature of the first temperature zone is 25-30 ℃, and the height is 30-50 cm; the temperature of the second temperature zone is 70-80 ℃, and the height of the second temperature zone is 20-40 cm.
2. The method for preparing the photocatalytic nanofiber membrane according to claim 1, wherein the heating rate during urea calcination is 15-20 ℃/min, and the urea is heated to 600-650 ℃ and calcined for 4-5 hours.
3. The preparation method of the photocatalytic nanofiber membrane according to claim 1, wherein the mass ratio of g-C 3N4 to ethanol, nickel nitrate hexahydrate and urea is 1 (20-40): 1-5.
4. The preparation method of the photocatalytic nanofiber membrane according to claim 1, wherein the mass ratio of chitosan, polyvinylpyrrolidone and acetic acid is1 (0.05-0.15): 50-100; the mass ratio of the spinning matrix to the g-C 3N4/NiO photocatalytic material is (8-15): 1.
5. A photocatalytic nanofiber membrane prepared by the method of any one of claims 1 to 4.
6. Use of the photocatalytic nanofiber membrane according to claim 5 for simultaneous adsorption and degradation of tetracycline antibiotics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410089886.5A CN117599834B (en) | 2024-01-23 | 2024-01-23 | Photocatalytic nanofiber membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410089886.5A CN117599834B (en) | 2024-01-23 | 2024-01-23 | Photocatalytic nanofiber membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117599834A CN117599834A (en) | 2024-02-27 |
| CN117599834B true CN117599834B (en) | 2024-05-07 |
Family
ID=89960188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410089886.5A Active CN117599834B (en) | 2024-01-23 | 2024-01-23 | Photocatalytic nanofiber membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117599834B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926053A (en) * | 2019-03-25 | 2019-06-25 | 中国地质大学（北京） | A kind of NiO/NiTiO3Composite nano-fiber membrane catalysis material |
| CN114632536A (en) * | 2022-04-01 | 2022-06-17 | 吉林化工学院 | NiCo with photocatalytic properties2O4/NiO/g-C3N4Nanotube preparation method and application |
| CN114797985A (en) * | 2022-03-25 | 2022-07-29 | 哈尔滨工程大学 | Flexible and recyclable C 3 N 4 ZIF-8 composite nanofiber photocatalytic film and preparation method thereof |
-
2024
- 2024-01-23 CN CN202410089886.5A patent/CN117599834B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926053A (en) * | 2019-03-25 | 2019-06-25 | 中国地质大学（北京） | A kind of NiO/NiTiO3Composite nano-fiber membrane catalysis material |
| CN114797985A (en) * | 2022-03-25 | 2022-07-29 | 哈尔滨工程大学 | Flexible and recyclable C 3 N 4 ZIF-8 composite nanofiber photocatalytic film and preparation method thereof |
| CN114632536A (en) * | 2022-04-01 | 2022-06-17 | 吉林化工学院 | NiCo with photocatalytic properties2O4/NiO/g-C3N4Nanotube preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117599834A (en) | 2024-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109235044B (en) | ZIF-8 loaded polyvinylidene fluoride nanofiber membrane and preparation method and application thereof | |
| CN111974453B (en) | Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof | |
| CN109577005A (en) | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification | |
| CN112076785B (en) | Carbon nitride/lanthanum hydroxide nanofiber membrane and preparation method and application thereof | |
| CN103225133A (en) | Active carbon fiber and preparation method thereof | |
| CN108147457B (en) | Method for preparing bismuth-based oxide nanosheets and application of bismuth-based oxide nanosheets | |
| CN113171800B (en) | Modified molecular sieve composite flexible ceramic nanofiber material and preparation method and application thereof | |
| CN110813306A (en) | Zinc ferrite/bismuth tungstate composite catalyst, preparation method thereof and application thereof in waste gas treatment | |
| CN111450902A (en) | Preparation method of antibacterial silver molybdate/MI L-101 (Fe, Zn) heterojunction photocatalytic film, product and application thereof | |
| CN111167455A (en) | Graphene-loaded cobalt-doped titanium dioxide photocatalyst and preparation method thereof | |
| CN117299206B (en) | Iron oxide/polyetherimide nanofiber catalytic membrane, preparation method and application thereof | |
| CN117599834B (en) | Photocatalytic nanofiber membrane and preparation method and application thereof | |
| CN103225132A (en) | Bioactive carbon fiber preparation method | |
| CN111203114A (en) | Multilayer bio-based hollow nanofiber water treatment membrane, preparation method and application thereof | |
| CN112718000B (en) | Organic-inorganic composite photocatalytic film and preparation method and application thereof | |
| CN114849712B (en) | Preparation method and application of porous carbon coated bimetallic oxide catalyst | |
| CN114561719B (en) | Cerium oxide/silicon oxide composite fiber material with fiber interweaved structure and preparation method and application thereof | |
| CN113828288B (en) | Alveolus-imitating double-layer nano-micro fiber membrane photocatalyst and preparation method thereof | |
| CN113413894A (en) | Preparation method of zinc ferrite electrostatic spinning membrane with photocatalytic antibacterial performance | |
| CN112458621A (en) | Load type nano cuprous oxide-nanofiber composite material and preparation method thereof | |
| CN113105033A (en) | Preparation method of special material for biological magnetized aquaculture filter material | |
| CN116926780A (en) | Silver-loaded porous carbon nanofiber catalytic degradation material and preparation method thereof | |
| CN111841660B (en) | Preparation of magnetic suspension 3D ozone catalytic microspheres and application thereof in aquaculture sewage | |
| CN117123254A (en) | Cobalt-nitrogen co-doped carbon nanofiber for high-efficiency peroxymonosulfate catalysis | |
| CN111992257B (en) | Modified perovskite hollow porous microsphere for catalytic degradation of antibiotics, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |