CN115106105B - Preparation method and application of ternary heterojunction photocatalytic film - Google Patents
Preparation method and application of ternary heterojunction photocatalytic film Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- 230000003115 biocidal effect Effects 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
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- 239000002135 nanosheet Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
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- 239000012528 membrane Substances 0.000 abstract description 62
- 238000000926 separation method Methods 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 238000001782 photodegradation Methods 0.000 abstract description 14
- 238000000967 suction filtration Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 230000004907 flux Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000004695 Polyether sulfone Substances 0.000 description 9
- 229920006393 polyether sulfone Polymers 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 8
- 229940088710 antibiotic agent Drugs 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- -1 hydroxyl free radical Chemical class 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 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 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- QYSPLQLAKJAUJT-UHFFFAOYSA-N piroxicam Chemical compound OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 QYSPLQLAKJAUJT-UHFFFAOYSA-N 0.000 description 1
- 229960002702 piroxicam Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- 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
- C02F2101/38—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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Abstract
The invention discloses a preparation method and application of a ternary heterojunction photocatalytic film. Preparing a BiOBr nano material by adopting a solvothermal method; chemically etching MAX phase through LiF+HCl mixed solution to obtain a two-dimensional MXene material with a clear lamellar structure; preparation of BiOBr/Bi by one-step hydrothermal method 2 MoO 6 An @ MXene ternary heterojunction composite; biOBr/Bi 2 MoO 6 Dispersing @ MXene powder in deionized water, ultrasonically stirring to uniformly disperse, and carrying out suction filtration on a precursor solution on a PES substrate by a vacuum-assisted self-assembly mode to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES ternary heterojunction photocatalysis composite membrane is applied to the treatment of antibiotic wastewater. The invention synthesizes a novel ternary heterojunction photocatalytic film material, and provides a practical basis and a reference value for developing a high-performance film separation material and constructing a novel photocatalytic composite film. From the perspective of exploring the structure and photocatalysis mechanism of the membrane material, the membrane separation efficiency and photodegradation capability are improved, and finally the purposes of greenness, environmental protection and wastewater treatment cost reduction are achieved.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method of a ternary heterojunction photocatalytic film, the ternary heterojunction photocatalytic film prepared by the preparation method and application of the ternary heterojunction photocatalytic film.
Background
The environmental pollution of antibiotics has attracted considerable attention, and tetracyclines and fluoroquinolones are often detected in soil/groundwater. Since most antibiotics have a stable chemical structure, conventional physicochemical and biological treatments cannot effectively remove them. Therefore, there is an urgent need to develop an efficient technique for decomposing antibiotics in water. The membrane separation technology has the characteristics of environmental protection, high separation efficiency, low energy consumption and the like, is known as the 21 st century water treatment technology, and can effectively remove antibiotics. However, the traditional membrane material has poor anti-pollution performance, and the formed membrane pollution not only shortens the service life of the membrane, but also increases the running cost. In addition, the permeability and selectivity of the membrane are mutually restricted, and further practical application of the membrane is limited. Therefore, the development of novel membrane materials and advanced membrane separation processes has important practical value and research significance.
MXene is a novel two-dimensional (2D) transition metal carbide or carbonitride that can be synthesized by chemical etching of MAX phase. The general formula of MXene is represented by M n+1 X n T x Wherein M is early transition metal element, X is carbon or nitrogen element, and T is active group attached to the surface. As a novel 2D material, the MXene has the characteristics of high specific surface area, conductivity, hydrophilicity, adjustable and controllable interlayer and the like, so that the membrane separation material based on the MXene has great development potential, and is widely focused by students in the aspects of membrane construction and design. In 2015, the professor Yury task group reported the preparation of MXene membranes and ion diffusion behavior for the first time, opening the door of MXene materials to the membrane separation world. Furthermore, pandeet et al utilize AgNO 3 From the reduction reaction, ag is grafted to the MXene surface to prepare the Ag@MXene/PVDF composite film. The addition of Ag shortens the water conveying path and leads the pure water flux to be from 118 L.m -2 ·h -1 ·bar -1 Up to 420 L.m -2 ·h -1 ·bar -1 . In addition, the membrane showed higher rejection rates for rhodamine B (79.9%), methyl green (92.3%) and bovine serum albumin (100%). Therefore, the two-dimensional MXene material has wide theoretical research and practical wastewater treatment prospects in the field of membrane separation material construction.
The Zhang subject group directly deposits 2D MXene nano-sheets on a Mixed Cellulose Ester (MCE) filtering membrane through a suction filtration device to construct an MXene/MCE deposition composite membrane. As the MXene has ultra-small interlayer spacing and plays a role of a nano filter, and the MCE has high porosity, the prepared MXene/MCE membrane has higher permeation flux (44.97 L.m -2 ·h -1 ) And has excellent removal rate (94.63 +/-3.8%) for methylene blue dye. The study also found that the effective removal of dye was attributable to the synergy between particle size selection screening, electrostatic repulsion of MXene, and high porosity of the matrix. However, the MXene acting as a membrane separation layer in this study was a monolayerOr a few layers of MXene which is etched by the HCI+LiF mixed solution is still in a multi-layer structure, is difficult to orderly stack on the surface of the membrane, and is easy to cause poor swelling resistance and undefined separation mechanism of the MXene membrane. Secondly, the composite film only feeds a smaller dye solution volume [ ]<30 mL) has excellent removing effect>98%) and less throughput, and is not satisfactory for practical industrial applications. The principle of the composite membrane for removing the dye is only that the interlayer spacing screening and the separation function are single, and the membrane separation technology is not coupled with other water treatment technologies (such as photocatalysis technology).
The He subject group was prepared by a simple solvothermal method using Bi (NO 3 ) 3 ·5H 2 O、Na 2 MoO 4 ·2H 2 O and CTAB are used as raw materials to directly precipitate and synthesize a flower-shaped BiOBr/Bi at room temperature 2 MoO 6 A composite material. Research by BET test method proves that flower-like BiOBr/Bi 2 MoO 6 The composite material has a mesoporous structure, and is observed by TEM (transmission electron microscope) to be BiOBr/Bi 2 MoO 6 The composite material is in a core-shell structure, the thickness of the shell layer is about 120nm, and the shell is composed of a large number of nano plates. The HRTEM image of the composite material had clear lattice fringes, indicating good crystallinity of the nanoplatelets, with adjacent facets at a lattice distance of about 0.40nm. Experimental results show that (BiOBr and Bi) 2 MoO 6 ) Compared with the composite material, the composite material has larger specific surface area and pore diameter, and has more excellent adsorption capacity to methylene blue (98%) and piroxicam B (90%) solutions. However, this technique involves only the adsorption of dye by the photocatalyst, and does not sufficiently exhibit the photocatalytic effect of the photocatalyst on contaminants. The powder photocatalyst mainly treats single pollutants, and is still to be researched for treating various pollutants in complex water environment. Secondly, the photocatalyst powder is easy to agglomerate in the experimental process, so that the effective specific surface area is reduced, and the adsorption effect is weakened. The powder photocatalytic material is difficult to recover, secondary pollution is easy to cause to degraded pollutants, and the expected effect cannot be achieved in practical application. From this, biOBr/Bi 2 MoO 6 The catalytic degradation capability of the binary heterojunction photocatalytic material is further improvedA lifting space.
Based on the analysis, a novel ternary heterojunction photocatalytic composite membrane with stable structure, high permeation flux and other comprehensive performances is urgently needed in the industry at present.
Disclosure of Invention
In view of the above-mentioned shortcomings, the present invention aims to construct a novel ternary heterojunction photocatalytic composite membrane with stable structure and comprehensive performances such as high permeation flux. Preparing a BiOBr nano material by adopting a solvothermal method; chemically etching MAX phase through LiF+HCl mixed solution to obtain a two-dimensional MXene material with a clear lamellar structure; preparation of BiOBr/Bi by one-step hydrothermal method 2 MoO 6 An @ MXene ternary heterojunction composite; biOBr/Bi 2 MoO 6 Dispersing @ MXene powder in deionized water, ultrasonically stirring to uniformly disperse, and carrying out suction filtration on a precursor solution on a PES substrate by a vacuum-assisted self-assembly mode to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES ternary heterojunction photocatalysis composite membrane is applied to the treatment of antibiotic wastewater. The invention synthesizes a novel ternary heterojunction photocatalytic film material, and provides a practical basis and a reference value for developing a high-performance film separation material and constructing a novel photocatalytic composite film. From the perspective of exploring the structure and photocatalysis mechanism of the membrane material, the membrane separation efficiency and photodegradation capability are improved, and finally the purposes of greenness, environmental protection and wastewater treatment cost reduction are achieved.
The invention is realized by the following technical scheme:
a method of preparing a ternary heterojunction photocatalytic film comprising:
1. preparation of MXene:
and chemically etching the MAX phase by adopting a LiF+HCl mixed solution to prepare the two-dimensional MXene material.
(1) 4g LiF was dissolved in 50mL HCl (12 mol/L) solution at normal temperature and pressure, and 2.5g Ti was dissolved in 3 AlC 2 The powder was added to the above solution and magnetically stirred at 25 ℃ for 24h.
(2) The resulting dispersion was repeatedly centrifuged at 3500rpm and washed with deionized water (DI) multiple times to neutralize the remaining acid until the solution supernatant had a pH of 6, while collecting the supernatant to obtain multi-layered MXene nanoplatelets.
(3) The resulting sample was dispersed in 50mL of deionized water, sonicated under nitrogen for 8 hours, and after the dispersion was centrifugally washed at 3500rpm, the resulting supernatant was collected, dried under vacuum freezing conditions and stored.
The main chemical reactions are as follows:
Ti 3 AlC 2 +3LiF+3HCl＝AlF 3 +3/2H 2 +Ti 3 C 2 +3LiCl (1-1)
Ti 3 C 2 +2H 2 O＝Ti 3 C 2 (OH) 2 +H 2 (1-2)
Ti 3 C 2 +2LiF+2HCl＝Ti 3 C 2 F 2 +H 2 +2LiCl (1-3)
and (3) stripping the MAX phase Al layer through a reaction (1-1), enabling the surface of the MXene to be attached with hydrophilic groups such as-OH, -F and=O through a reaction (1-2) and a reaction (1-3), neutralizing redundant electrons on the surface of the Ti metal, and obtaining the MXene material with a stable nano-sheet structure.
2. Preparation of BiOBr
The BiOBr powder is prepared by a solvothermal method.
(1) 2mmol Bi (NO) was accurately weighed out by analytical balance 3 ) 3 ·5H 2 O, dispersed in 10mL of ethylene glycol, sonicated at room temperature for 15min, was used as solution A.
(2) 1mmol CTAB was weighed accurately with an analytical balance, dispersed in 10mL of ethylene glycol, and sonicated at room temperature for 15min as a B solution.
(3) Solution B was slowly added to solution a and mixed ultrasonically at room temperature for 15min to disperse uniformly.
(4) After magnetically stirring the mixed solution at room temperature for 30min, the mixed solution was poured into a 50mL reaction kettle and reacted at 160℃for 12h.
(5) And (3) washing the obtained product with deionized water and absolute ethyl alcohol alternately for 3 times, and drying in a blast drying oven at 60 ℃ to obtain BiOBr powder.
3. Preparation of BiOBr/Bi2MoO6@MXene heterojunction
Preparation of BiOBr/Bi by hydrothermal method 2 MoO 6 @ MXene heterojunction.
(1) 0.1617g Bi (NO) was weighed out accurately 3 ) 3 ·5H 2 O and 0.0404gNa 2 MoO 6 ·2H 2 O, dispersed in 10mL of ethylene glycol, respectively, was sonicated at room temperature for 15min, respectively, as solutions A and B.
(2) 20 mM Xene dispersion (0.5 mg/L) was accurately measured and dispersed in 10mL of ethylene glycol, and sonicated at 30℃for 15min as a C solution.
(3) A certain amount of the obtained BiOBr powder was accurately weighed and dispersed in 10mL of ethylene glycol, and the mixture was sonicated at room temperature for 15min to obtain a D solution.
(4) The B, C, D solution was slowly added to the A solution in sequence, mixed sonicated at 30℃for 15min.
(5) After magnetically stirring the mixed solution at room temperature for 30min, the mixed solution was poured into a 100mL reaction kettle and reacted at 160℃for 12h.
(6) The obtained product is respectively washed for 3 times by deionized water and absolute ethyl alcohol alternately, and then dried in a vacuum drying oven at 60 ℃ to obtain BiOBr/Bi 2 MoO 6 Nano material of @ MXene heterojunction and binary heterojunction Bi without BiOBr added 2 MoO 6 @ MXene nanomaterial.
4. Construction of ternary heterojunction photocatalysis composite film
(1) 30mgBiOBr/Bi at normal temperature and pressure 2 MoO 6 Dissolving @ MXene ternary heterojunction powder in 100mL deionized water, and ultrasonic stirring at 30deg.C for 30min to obtain uniformly dispersed BiOBr/Bi 2 MoO 6 @ MXene precursor solution.
(2) Then slowly pumping and filtering the precursor solution onto PES film (aperture of 0.22 μm) under the pressure of 0.1MPa by adopting a vacuum-assisted self-assembly method to construct 3 BiOBr/Bi with different proportions 2 MoO 6 The composition of the @ MXene/PES photocatalytic composite film is shown in Table 1.
TABLE 1
Subsequent experiments show that the M4 membrane in the table 1 has the best catalytic capability and the permeability of the composite membrane is the best.
The invention has the beneficial effects that:
the invention provides more beneficial effects by constructing a brand new ternary heterojunction photocatalytic composite membrane, and the method mainly comprises the following steps:
1. the photocatalytic capability of the composite film is endowed. The membrane separation technology cannot fundamentally remove pollutants, and the pollutants are easy to deposit on the surface and micropores of the membrane to form membrane pollution, so that the separation efficiency of the membrane is reduced. The invention couples the photocatalysis technology and the membrane separation technology, designs and constructs the photocatalysis composite membrane with separation and photodegradation capabilities. Experimental results show that the ternary heterojunction composite membrane (M2-M4) achieves better photodegradation effect than the binary heterojunction composite membrane (M1), and the pure water flux of the photocatalysis membrane (M4) with the optimal proportion is 1117.13 L.m under the driving of the pressure of 0.1MPa 2 ·h -1 ·bar -1 The retention rates of TC and CIP are 26.76% and 41.29%, respectively, and the photodegradation rate is as high as 92.16% and 90.30% after being irradiated for 8 hours under visible light. Compared with the binary heterojunction photocatalysis composite membrane (M1), the pure water flux of M1 is only 438.56 L.m 2 ·h -1 ·bar -1 The retention rates for TC and CIP were 23.55% and 42.91%, respectively, and the photodegradation rates were 83.62% and 80.11%. Therefore, the modification scheme obviously improves the hydrophilicity and photocatalytic degradation capability of the membrane, and provides a certain reference value for developing novel ternary heterojunction photocatalytic membrane materials.
2. The contribution of various active groups in the photodegradation process of pollutants is deeply analyzed through an active species capture experiment. Isopropyl alcohol (IPA), p-Benzoquinone (BQ) and disodium ethylenediamine tetraacetate (EDTA-2 Na) are respectively used as active hydroxyl free radical (OH) and superoxide free radical (O) 2 - ) And cavity (h) + ) Is a capture agent of (a). Adding it into solution containing antibiotic (TC), irradiating with visible light for 8 hr, and calculating photodegradation antibiotic with different capture agentsInfluence of the plain effect. The results show that the removal rate of TC is inhibited to a certain extent, and is respectively reduced by 16.04 percent (OH) and 39.83 percent (O) 2 - ) And 18.93% (h) + ). The results show that the active group is O 2 - Plays the most important role in the photocatalytic degradation of TC.
In general, the modification scheme of the ternary heterojunction not only enlarges the separation channel of the membrane, so that the permeability of the composite membrane is obviously improved, but also the photocatalytic capability of the composite membrane is endowed, the effective photodegradation removal of the membrane to the antibiotic wastewater is realized, and a reference basis is provided for constructing the composite membrane with high permeation flux and photocatalytic degradation capability.
Detailed Description
Abbreviations and key term definitions:
MAX phase (Ti) 3 AlC 2 )，MXene(Ti 3 C 2 T x ) LiF (lithium fluoride), HCl (hydrochloric acid), bi 2 MoO 6 Bismuth molybdate, biOBr, bi (NO 3 ) 3 ·5H 2 O (bismuth nitrate pentahydrate), na 2 MoO 6 ·2H 2 O (sodium molybdate dihydrate), CTAB (cetyltrimethylammonium bromide), PES (polyethersulfone), TC (tetracycline hydrochloride), CIP (CIP).
Example 1
A method of preparing a ternary heterojunction photocatalytic film comprising:
1. preparation of MXene:
and chemically etching the MAX phase by adopting a LiF+HCl mixed solution to prepare the two-dimensional MXene material.
(1) 4g LiF was dissolved in 50mL HCl (12 mol/L) solution at normal temperature and pressure, and 2.5g Ti was dissolved in 3 AlC 2 The powder was added to the above solution and magnetically stirred at 25 ℃ for 24h.
(2) The resulting dispersion was repeatedly centrifuged at 3500rpm and washed with deionized water (DI) multiple times to neutralize the remaining acid until the solution supernatant had a pH of 6, while collecting the supernatant to obtain multi-layered MXene nanoplatelets.
(3) The resulting sample was dispersed in 50mL of deionized water, sonicated under nitrogen for 8 hours, and after the dispersion was centrifugally washed at 3500rpm, the resulting supernatant was collected, dried under vacuum freezing conditions and stored.
The main chemical reactions are as follows:
Ti 3 AlC 2 +3LiF+3HCl＝AlF 3 +3/2H 2 +Ti 3 C 2 +3LiCl (1-1)
Ti 3 C 2 +2H 2 O＝Ti 3 C 2 (OH) 2 +H 2 (1-2)
Ti 3 C 2 +2LiF+2HCl＝Ti 3 C 2 F 2 +H 2 +2LiCl (1-3)
and (3) stripping the MAX phase Al layer through a reaction (1-1), enabling the surface of the MXene to be attached with hydrophilic groups such as-OH, -F and=O through a reaction (1-2) and a reaction (1-3), neutralizing redundant electrons on the surface of the Ti metal, and obtaining the MXene material with a stable nano-sheet structure.
2. Preparation of BiOBr
The BiOBr powder is prepared by a solvothermal method.
(1) 2mmol Bi (NO) was accurately weighed out by analytical balance 3 ) 3 ·5H 2 O, dispersed in 10mL of ethylene glycol, sonicated at room temperature for 15min, was used as solution A.
(2) 1mmol CTAB was weighed accurately with an analytical balance, dispersed in 10mL of ethylene glycol, and sonicated at room temperature for 15min as a B solution.
(3) Solution B was slowly added to solution a and mixed ultrasonically at room temperature for 15min to disperse uniformly.
(4) After magnetically stirring the mixed solution at room temperature for 30min, the mixed solution was poured into a 50mL reaction kettle and reacted at 160℃for 12h.
(5) And (3) washing the obtained product with deionized water and absolute ethyl alcohol alternately for 3 times, and drying in a blast drying oven at 60 ℃ to obtain BiOBr powder.
3、BiOBr/Bi 2 MoO 6 Preparation of @ MXene heterojunction
Preparation of BiOBr/Bi by hydrothermal method 2 MoO 6 @ MXene heterojunction.
(1) 0.1617g Bi (NO) was weighed out accurately 3 ) 3 ·5H 2 O and 0.0404gNa 2 MoO 6 ·2H 2 O, dispersed in 10mL of ethylene glycol, respectively, was sonicated at room temperature for 15min, respectively, as solutions A and B.
(2) 20 mM Xene dispersion (0.5 mg/L) was accurately measured and dispersed in 10mL of ethylene glycol, and sonicated at 30℃for 15min as a C solution.
(3) A certain amount of the obtained BiOBr powder was accurately weighed and dispersed in 10mL of ethylene glycol, and the mixture was sonicated at room temperature for 15min to obtain a D solution.
(4) The B, C, D solution was slowly added to the A solution in sequence, mixed sonicated at 30℃for 15min.
(5) After magnetically stirring the mixed solution at room temperature for 30min, the mixed solution was poured into a 100mL reaction kettle and reacted at 160℃for 12h.
(6) The obtained product is respectively washed for 3 times by deionized water and absolute ethyl alcohol alternately, and then dried in a vacuum drying oven at 60 ℃ to obtain BiOBr/Bi 2 MoO 6 Nano material of @ MXene heterojunction and binary heterojunction Bi without BiOBr added 2 MoO 6 @ MXene nanomaterial.
4. Construction of ternary heterojunction photocatalysis composite film
(1) 30mgBiOBr/Bi at normal temperature and pressure 2 MoO 6 Dissolving @ MXene ternary heterojunction powder in 100mL deionized water, and ultrasonic stirring at 30deg.C for 30min to obtain uniformly dispersed BiOBr/Bi 2 MoO 6 @ MXene precursor solution.
(2) Then slowly pumping and filtering the precursor solution onto PES film (aperture of 0.22 μm) under the pressure of 0.1MPa by adopting a vacuum-assisted self-assembly method to construct BiOBr/Bi 2 MoO 6 Composition of @ MXene/PES photocatalytic composite film: bi (Bi) 2 MoO 6 The mass ratio of the MXene to the BiOBr is 100:10:10, namely the M2 film.
Example 2
The preparation was the same as in example 1, except that Bi 2 MoO 6 The mass ratio of the MXene to the BiOBr is 100:10:20,i.e. M3 film.
Example 3
The preparation was the same as in example 1, except that Bi 2 MoO 6 The mass ratio of the MXene to the BiOBr is 100:10:40, namely the M4 film.
Comparative example 1
The preparation was the same as in example 1, except that Bi 2 MoO 6 The mass ratio of the MXene to the BiOBr is 100:10:0, namely the M1 film.
Test example 1
Photocatalytic Capacity verification
The photocatalytic capacity of the ternary heterojunction photocatalytic film was evaluated by means of a self-made photocatalytic device. The specific method comprises the following steps: firstly, penetrating 100mL of deionized water under 0.1MPa by means of a vacuum filtration device, recording the required time, and calculating the pure water flux of the membrane, wherein the effective area of the membrane is 12.56cm 2 . At the same time, 100mL of antibiotic solution was then permeated by means of a vacuum filtration device and the rejection rate of the membrane was tested. Then, the membrane is taken out of the vacuum filtration device, immersed in the permeate liquid for photocatalytic degradation experiments, continuously irradiated for 8 hours under visible light, collected for 5mL of reaction liquid per hour, and finally measured by measuring the absorbance of different antibiotics in characteristic peaks (TC: 356nm; CIP:272 nm) by an ultraviolet spectrophotometer to measure the concentration of the antibiotics.
Experimental results show that the ternary heterojunction composite membrane (M2-M4) achieves better photodegradation effect than the binary heterojunction composite membrane (M1), and the pure water flux of the photocatalysis membrane (M4) with the optimal proportion is 1117.13 L.m under the driving of the pressure of 0.1MPa 2 ·h -1 ·bar -1 The retention rates of TC and CIP are 26.76% and 41.29%, respectively, and the photodegradation rate is as high as 92.16% and 90.30% after being irradiated for 8 hours under visible light. Compared with the binary heterojunction photocatalysis composite membrane (M1), the pure water flux of M1 is only 438.56 L.m 2 ·h -1 ·bar -1 The retention rates for TC and CIP were 23.55% and 42.91%, respectively, and the photodegradation rates were 83.62% and 80.11%. Therefore, the modification scheme obviously improves the hydrophilicity and photocatalytic degradation capability of the membrane, and provides a certain reference value for developing novel ternary heterojunction photocatalytic membrane materials.
Test example 2
Contribution of reactive groups in the photodegradation of contaminants
Isopropyl alcohol (IPA), p-Benzoquinone (BQ) and disodium ethylenediamine tetraacetate (EDTA-2 Na) are respectively used as active hydroxyl free radical (OH) and superoxide free radical (O) 2 - ) And cavity (h) + ) Is a capture agent of (a). It was added to a solution containing antibiotics (TC) and after irradiation under visible light for 8 hours, the effect of the different capture agents on the effect of photodegradation of antibiotics was calculated. The results show that the removal rate of TC is inhibited to a certain extent, and is respectively reduced by 16.04 percent (OH) and 39.83 percent (O) 2 - ) And 18.93% (h) + ). The results show that the active group is O 2 - Plays the most important role in the photocatalytic degradation of TC.
In the complete technical scheme of the invention, the ternary heterojunction photocatalytic composite film can still be prepared by the following ways, and the purpose of the invention is realized:
1. if other people adopt HF and NH except for etching MAX phase by adopting LiF+HCl mixed reagent 4 HF 2 NaOH and H 2 SO 4 And the MXene is prepared by etching in the same way, other steps are consistent with the technical scheme of the invention, and the ternary heterojunction photocatalytic composite film is also prepared, so that the purpose of the invention is realized.
2. The invention adopts PES film as the supporting layer of the composite film, if other people adopt organic polymer film materials such as Cellulose Acetate (CA) film, polyvinylidene fluoride (PVDF) and the like as the supporting layer, other steps (such as Bi 2 MoO 6 And preparation of BiOBr, preparation of MXene and mixing proportion) are consistent with the technical scheme of the invention, and ternary heterojunction photocatalytic composite films can be prepared, so that the purpose of the invention is achieved.
3. The invention adopts Bi 2 MoO 6 And BiOBr as photocatalytic material, if other people use TiO 2 ，g-C 3 N 4 ZnO and other bismuth materials are used as photocatalysis materials, other steps are consistent with the technical proposal of the invention, and ternary heterojunction photocatalysis composite films can be prepared, thereby realizing the purpose of the invention.
4. In the invention, the ternary heterojunction nano material is synthesized in situ by adopting a hydrothermal method, and if other people adopt a direct mixing method, other steps (Bi 2 MoO 6 The mixing proportion of MXene and BiOBr, and the suction filtration stacking method) are consistent with my invention scheme, and ternary heterojunction photocatalytic composite films can be prepared, so that the purpose of the invention is achieved.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (6)
1. A method of preparing a ternary heterojunction photocatalytic film comprising:
(1) And chemically etching the MAX phase by adopting LiF+HCl mixed solution to prepare the two-dimensional MXene material:
(1-1) dissolving 4g LiF in 50mL of 12mol/L HCl solution at normal temperature and pressure, and adding 2.5g Ti thereto 3 AlC 2 Magnetically stirring the powder at 25 ℃ for 24 hours to obtain a dispersion liquid;
(1-2) repeatedly centrifuging the dispersion at 3500rpm, repeatedly washing with deionized water, and collecting the supernatant to obtain a multi-layered MXene nanoplatelet;
(1-3) dispersing the multi-layer MXene nano-sheets in 50mL of deionized water, carrying out ultrasonic stripping for 8 hours in a nitrogen environment, centrifugally cleaning the dispersion liquid at 3500rpm for multiple times, collecting supernatant, and drying under vacuum freezing conditions to obtain a two-dimensional MXene material for storage;
(2) The BiOBr powder is prepared by a solvothermal method:
(2-1) weighing 2mmol Bi (NO) 3 ) 3 ·5H 2 O, dispersing the solution in 10mL of ethylene glycol, and performing ultrasonic treatment at room temperature for 15min to obtain solution A;
(2-2) 1mmol of CTAB was weighed, dispersed in 10mL of ethylene glycol, and sonicated at room temperature for 15min as a B solution;
(2-3) slowly adding the solution B into the solution A, and carrying out ultrasonic mixing at room temperature for 15min to obtain a solution C;
(2-4) magnetically stirring the solution C for 30min at room temperature, pouring the solution C into a 50mL reaction kettle, and reacting for 12h at 160 ℃ to obtain a product D;
(2-5) washing the D product with deionized water and absolute ethyl alcohol alternately for 3 times respectively, and drying at 60 ℃ in a blast drying oven to obtain BiOBr powder;
(3) Preparation of BiOBr/Bi by hydrothermal method 2 MoO 6 @ MXene heterojunction:
(3-1) weighing 0.1617g Bi (NO) 3 ) 3 ·5H 2 O and 0.0404g Na 2 MoO 6 ·2H 2 O, dispersing in 10mL of ethylene glycol respectively, and respectively performing ultrasonic treatment at room temperature for 15min to obtain solution A and solution B;
(3-2) 20mL of the MXene dispersion liquid with the concentration of 0.5mg/L is measured and dispersed in 10mL of ethylene glycol, and ultrasonic treatment is carried out at 30 ℃ for 15min to obtain a solution C;
(3-3) weighing 40mgBiOBr powder, dispersing in 10mL of ethylene glycol, and performing ultrasonic treatment at room temperature for 15min to obtain solution D;
(3-4) sequentially and slowly adding the B, C, D solution into the solution A, and mixing and ultrasonic treatment at 30 ℃ for 15min to obtain a solution E;
(3-5) magnetically stirring the E solution for 30min at room temperature, pouring the E solution into a 100mL reaction kettle, and reacting for 12h at 160 ℃ to obtain an F product;
(3-6) alternately washing F product with deionized water and absolute ethyl alcohol for 3 times, respectively, and oven drying at 60deg.C in vacuum drying oven to obtain BiOBr/Bi 2 MoO 6 An @ MXene heterojunction nanomaterial;
(4) Construction of a ternary heterojunction photocatalytic composite film:
(4-1) 30mgBiOBr/Bi at ordinary temperature and pressure 2 MoO 6 Dissolving @ MXene ternary heterojunction powder in 100mL of deionized water, and performing ultrasonic stirring treatment at 30 ℃ for 30min to obtain BiOBr/Bi 2 MoO 6 An @ MXene precursor solution;
(4-2) vacuum assisted self-assembly method under 0.1MPa pressure, biOBr/Bi 2 MoO 6 Slowly filtering the @ MXene precursor solution onto a PES film to construct BiOBr/Bi 2 MoO 6 @ MXene/PES photocatalytic composite film.
2. The method of manufacturing according to claim 1, wherein:
and (3) repeatedly washing the deionized water in the step (1-2) until the pH value of the solution supernatant is 6.
3. The method of manufacturing according to claim 1, wherein:
the pressure in the step (4-2) is 0.1MPa, and the pore diameter of the PES film is 0.22 μm.
4. The method of manufacturing according to claim 1, wherein:
step (4-2) the BiOBr/Bi 2 MoO 6 Bi in @ MXene/PES photocatalytic composite film 2 MoO 6 The mass ratio of the MXene to the BiOBr is 100:10:40.
5. A ternary heterojunction photocatalytic film produced according to the production method of any one of claims 1 to 4.
6. Use of the ternary heterojunction photocatalytic film according to claim 5 in antibiotic wastewater treatment.
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