CN115106105A - Preparation method and application of ternary heterojunction photocatalytic film - Google Patents
Preparation method and application of ternary heterojunction photocatalytic film Download PDFInfo
- Publication number
- CN115106105A CN115106105A CN202210660174.5A CN202210660174A CN115106105A CN 115106105 A CN115106105 A CN 115106105A CN 202210660174 A CN202210660174 A CN 202210660174A CN 115106105 A CN115106105 A CN 115106105A
- Authority
- CN
- China
- Prior art keywords
- mxene
- solution
- biobr
- moo
- membrane
- 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.)
- Granted
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 230000003115 biocidal effect Effects 0.000 claims abstract description 9
- 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
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 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
- 239000002135 nanosheet Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000003860 storage Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 19
- 238000001782 photodegradation Methods 0.000 abstract description 12
- 230000007246 mechanism Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 18
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 14
- 239000004695 Polyether sulfone Substances 0.000 description 11
- 229920006393 polyether sulfone Polymers 0.000 description 11
- 230000004907 flux Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 229940088710 antibiotic agent Drugs 0.000 description 7
- 229960003405 ciprofloxacin Drugs 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 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
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration 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
- 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 hydroxyl free radical Chemical class 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
- 238000005086 pumping Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 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
- 230000003373 anti-fouling effect Effects 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
- 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
- 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
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012530 fluid Substances 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
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009285 membrane fouling Methods 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
- 239000000203 mixture Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 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
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 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
- 230000009044 synergistic interaction 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
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 the MAX phase by using LiF + HCl mixed solution to obtain a two-dimensional MXene material with a clear lamellar structure; using one-step waterThermal method for preparing BiOBr/Bi 2 MoO 6 @ MXene ternary heterojunction composite material; BiOBr/Bi 2 MoO 6 The @ MXene powder is dispersed in deionized water and ultrasonically stirred to be uniformly dispersed, and the precursor solution is filtered on a PES substrate in a vacuum-assisted self-assembly mode to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES ternary heterojunction photocatalytic composite membrane is applied to treatment of antibiotic wastewater. The invention synthesizes a novel ternary heterojunction photocatalytic film material, and provides practical basis and reference value for developing high-performance film separation materials and constructing novel photocatalytic composite films. From the viewpoint of exploring the structure and the photocatalysis mechanism of the membrane material, the method aims to improve the separation efficiency and the photodegradation capability of the membrane and finally achieve the aims of being green and environment-friendly and reducing the wastewater treatment cost.
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 pollution of antibiotic drugs to the environment has attracted people's attention, and tetracyclines and fluoroquinolones antibiotics can be detected in soil/groundwater. Since most antibiotics have stable chemical structures, they cannot be removed effectively by conventional physicochemical and biological treatments. Therefore, it is urgent to develop a highly 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 water treatment technology in the 21 st century, and can effectively remove antibiotics. However, conventional membrane materials have poor anti-fouling properties, and the resulting membrane fouling not only shortens the membrane life but also increases operating costs. In addition, the permeability and selectivity of the membrane are mutually restricted, which limits further practical applications. Therefore, the development of novel membrane materials and advanced membrane separation processes has important practical value and research significance.
MXene is a new type of two-dimensional (2D) transition metal carbide or carbonitride that can be synthesized by chemical etching of the MAX phase. MXene has the general formula M n+1 X n T x Wherein M is an early transition metal element, X is carbon or nitrogen, and T is a surface-attached active group. As a novel 2D material, MXene has the characteristics of high specific surface area, conductivity, hydrophilicity, interlayer adjustability, controllability and the like, so that the MXene-based membrane separation material has great development potential and draws wide attention of scholars in the aspects of membrane construction and design. In 2015, the problem group taught by Yury reports the preparation and ion diffusion behavior of MXene film for the first time, and opens the door of MXene material to the world of membrane separation. In addition, Pandeyet et al utilize AgNO 3 And (3) carrying out self-reduction reaction, and grafting Ag to the surface of MXene to prepare the Ag @ MXene/PVDF composite membrane. The addition of Ag shortens the water transportation path and ensures that the pure water flux is from 118 L.m -2 ·h -1 ·bar -1 Increased to 420 L.m -2 ·h -1 ·bar -1 . In addition, the membrane showed high 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 actual wastewater treatment prospects in the field of membrane separation material construction.
The Zhang task group directly deposits 2D MXene nanosheets on a Mixed Cellulose Ester (MCE) filtering membrane through a suction filtration device to construct an MXene/MCE deposition composite membrane. As MXene has ultra-small interlayer spacing and functions as a nano filter, and 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%) to methylene blue dye. The study also found that the effective removal of dye can be attributed to a synergistic interaction between the particle size selective sieving, the electrostatic repulsion of MXene and the high porosity of the matrix. However, the MXene serving as a membrane separation layer in the research is single-layer or few-layer, and the MXene after being etched by the HCI + LiF mixed solution is still in a multi-layer structure, so that the MXene is difficult to orderly stack on the surface of the membrane, and the MXene membrane has poor swelling resistanceThe mechanism of separation is unclear. Second, the composite membrane only works for a small volume of dye feed solution: (<30mL) had excellent removing effect (>98%), the processing amount is small, and the practical industrial application cannot be satisfied. The dye removal principle of the composite membrane is only interlayer spacing screening and single separation function, and the membrane separation technology is not coupled with other water treatment technologies (such as photocatalysis technology).
He group uses a simple solvothermal method with Bi (NO) 3 ) 3 ·5H 2 O、Na 2 MoO 4 ·2H 2 O and CTAB are taken as raw materials to directly precipitate and synthesize a flower-shaped BiOBr/Bi 2 MoO 6 A composite material. The BET test method is adopted to research and confirm the flower-shaped BiOBr/Bi 2 MoO 6 The composite material has a mesoporous structure, and BiOBr/Bi is observed by adopting a TEM (transmission electron microscope) 2 MoO 6 The composite material is of a core-shell structure, the thickness of a shell layer is about 120nm, and a shell is formed by a large number of nano plates. The HRTEM image of the composite material has clear lattice stripes, which shows that the nanosheets have good crystallinity, and the lattice distance between adjacent planes is about 0.40 nm. The experimental results show that (BiOBr and Bi) with single component 2 MoO 6 ) Compared with the composite material, the composite material has larger specific surface area and pore size, and shows more excellent adsorption capacity to methylene blue (98%) and pyroxene B (90%) solutions. However, this technique only involves the adsorption of the photocatalyst to the dye, and does not sufficiently exhibit the photocatalytic effect of the photocatalyst on the contaminants. The powder photocatalyst mainly treats single pollutants, and the treatment of various pollutants in a complex water environment needs to be researched. 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, is easy to cause secondary pollution to degraded pollutants, and cannot achieve the expected effect in practical application. Thus, BiOBr/Bi 2 MoO 6 The catalytic degradation capability of the binary heterojunction photocatalytic material has a further improved space.
Based on the analysis, a novel ternary heterojunction photocatalytic composite membrane with stable structure, high permeation flux and comprehensive performance is urgently needed in the industry at present.
Disclosure of Invention
In view of the above disadvantages, the present invention aims to construct a novel ternary heterojunction photocatalytic composite membrane with stable structure, high permeation flux and comprehensive properties. Preparing a BiOBr nano material by adopting a solvothermal method; chemically etching the MAX phase by using LiF + HCl mixed solution to obtain a two-dimensional MXene material with a clear lamellar structure; BiOBr/Bi preparation by adopting one-step hydrothermal method 2 MoO 6 @ MXene ternary heterojunction composite material; BiOBr/Bi 2 MoO 6 The @ MXene powder is dispersed in deionized water and ultrasonically stirred to be uniformly dispersed, and the precursor solution is filtered on a PES substrate in a vacuum-assisted self-assembly mode to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES ternary heterojunction photocatalytic composite membrane is applied to treatment of antibiotic wastewater. The invention synthesizes a novel ternary heterojunction photocatalytic film material, and provides practical basis and reference value for developing high-performance film separation materials and constructing novel photocatalytic composite films. From the viewpoint of exploring the structure and the photocatalysis mechanism of the membrane material, the method aims to improve the separation efficiency and the photodegradation capability of the membrane and finally achieve the aims of being green and environment-friendly and reducing the wastewater treatment cost.
The invention is realized by the following technical scheme:
a preparation method of a ternary heterojunction photocatalytic film comprises the following steps:
1. preparation of MXene:
and chemically etching the MAX phase by using LiF + HCl mixed solution to prepare the two-dimensional MXene material.
[ 4g of LiF was dissolved in 50mL of HCl (12mol/L) solution at room temperature under normal pressure, and 2.5g of Ti was added 3 AlC 2 The powder was added to the above solution and magnetically stirred at a temperature of 25 ℃ for 24 h.
Repeatedly centrifuging the generated dispersion liquid at 3500rpm, washing the dispersion liquid for multiple times by using deionized water (DI) to neutralize the residual acid until the pH value of the solution supernatant is 6, and collecting the supernatant to obtain the multi-layer MXene nanosheets.
Dispersing the obtained sample in 50mL of deionized water, ultrasonically stripping for 8h in a nitrogen environment, centrifuging and cleaning the dispersion liquid for multiple times at 3500rpm, collecting the obtained supernatant, drying under a vacuum freezing condition and storing.
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)
the Al layer of the MAX phase is stripped through the reaction (1-1), and hydrophilic groups such as-OH, -F and ═ O are attached to the surface of MXene through the reactions (1-2) and (1-3), so that excessive electrons on the surface of the Ti metal are neutralized, and the obtained MXene material has a stable nanosheet structure.
2. Preparation of BiOBr
The BiOBr powder is prepared by a solvothermal method.
Firstly, accurately weighing 2mmol Bi (NO) by using an analytical balance 3 ) 3 ·5H 2 O, dispersing it in 10mL of ethylene glycol, and sonicating for 15min at room temperature to obtain solution A.
② accurately weighing 1mmol CTAB by an analytical balance, dispersing the CTAB in 10mL of glycol, and carrying out ultrasonic treatment at room temperature for 15min to obtain a solution B.
③ the solution B is slowly added into the solution A, and ultrasonic mixing is carried out for 15min at room temperature to disperse evenly.
Fourthly, the mixed solution is magnetically stirred for 30min at room temperature and then poured into a 50mL reaction kettle to react for 12h at 160 ℃.
And fifthly, washing the obtained product respectively with deionized water and absolute ethyl alcohol for 3 times, and drying in a forced air 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.
Precisely weighing 0.1617g Bi (NO) 3 ) 3 ·5H 2 O and 0.0404gNa 2 MoO 6 ·2H 2 O, dispersed in 10mL of ethylene glycol, and sonicated at room temperature for 15min, respectively, as solutions A and B.
② accurately measuring 20mL of the Xene dispersion liquid (0.5mg/L) to be dispersed in 10mL of glycol, and performing ultrasonic treatment at 30 ℃ for 15min to obtain a solution C.
Thirdly, accurately weighing a certain amount of BiOBr powder obtained by the previous step, dispersing the BiOBr powder in 10mL of glycol, and performing ultrasonic treatment at room temperature for 15min to obtain a solution D.
And fourthly, slowly adding the B, C, D solution into the A solution in turn, and mixing and carrying out ultrasonic treatment for 15min at the temperature of 30 ℃.
Fifthly, the mixed solution is magnetically stirred for 30min at room temperature and then poured into a 100mL reaction kettle to react for 12h at 160 ℃.
Sixthly, washing the obtained product by deionized water and absolute ethyl alcohol respectively for 3 times, and drying the product in a vacuum drying oven at 60 ℃ to obtain BiOBr/Bi 2 MoO 6 @ MXene heterojunction nano material and binary heterojunction Bi without BiOBr 2 MoO 6 @ MXene nano material.
4. Construction of ternary heterojunction photocatalytic composite film
Under normal temperature and pressure, 30mgBiOBr/Bi 2 MoO 6 Dissolving the @ MXene ternary heterojunction powder in 100mL of deionized water, and performing ultrasonic stirring treatment at 30 ℃ for 30min to obtain uniformly dispersed BiOBr/Bi 2 MoO 6 @ MXene precursor solution.
Secondly, slowly pumping and filtering the precursor solution to a PES (polyether sulfone) membrane (with the aperture of 0.22 mu m) by adopting a vacuum-assisted self-assembly method under the pressure of 0.1MPa to construct 3 BiOBr/Bi with different proportions 2 MoO 6 The composition of the @ MXene/PES photocatalytic composite membrane is shown in Table 1.
TABLE 1
Subsequent experiments show that the M4 film in the table 1 has the best catalytic capability and the permeability of the composite film 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 film, which is mainly expressed as follows:
1. endows the composite membrane with photocatalytic capability. Membrane separation techniques cannot remove contaminants fundamentally, and contaminants are easily deposited on the membrane surface and micropores to form membrane contaminants, thereby reducing the separation efficiency of the membrane. The invention couples a photocatalysis technology with a membrane separation technology, designs and constructs a photocatalysis composite membrane with separation and photodegradation capabilities. Experimental results show that the ternary heterojunction composite films (M2-M4) achieve better photodegradation effect than the binary heterojunction composite films (M1), and the pure water flux of the photocatalytic film (M4) with the optimal proportion is 1117.13 L.m under the drive of 0.1MPa pressure 2 ·h -1 ·bar -1 The retention rates of TC and CIP are respectively 26.76% and 41.29%, and after the light irradiation is carried out for 8 hours under visible light, the light degradation rates are as high as 92.16% and 90.30%. Compared with a binary heterojunction photocatalytic composite membrane (M1), the pure water flux of M1 is only 438.56L 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 the photocatalytic degradation capability of the membrane and provides a certain reference value for developing a novel ternary heterojunction photocatalytic membrane material.
2. The contribution of various active groups in the process of photodegradation of pollutants is deeply analyzed through active species capture experiments. Isopropanol (IPA), p-Benzoquinone (BQ) and ethylene diamine tetraacetic acid (EDTA-2Na) are respectively used as active groups of hydroxyl free radical (. OH) and superoxide free radical (. O) 2 - ) And a cavity (h) + ) The capturing agent of (1). The method is added into a solution containing the antibiotic (TC), and after the solution is irradiated under visible light for 8 hours, the influence of different capture agents on the effect of photodegradation of the antibiotic is calculated. As a result, the TC removal rates were suppressed to some extent, and decreased by 16.04% (. OH) and 39.83% (. O), respectively 2 - ) And 18.93% (h) + ). The results show that the active group O 2 - Plays the most important role in the process of photocatalytic degradation of TC.
Generally speaking, the modification scheme of the ternary heterojunction not only enlarges the separation channel of the membrane, obviously improves the permeability of the composite membrane, but also endows the composite membrane with photocatalytic capability, realizes the effective photodegradation removal of the membrane on the antibiotic wastewater, and provides reference basis 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 (bismuth oxybromide), 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 (ciprofloxacin).
Example 1
A preparation method of a ternary heterojunction photocatalytic film comprises the following steps:
1. preparation of MXene:
and chemically etching the MAX phase by using LiF + HCl mixed solution to prepare the two-dimensional MXene material.
[ 4g of LiF was dissolved in 50mL of HCl (12mol/L) solution at room temperature under normal pressure, and 2.5g of Ti was added 3 AlC 2 The powder was added to the above solution and stirred magnetically for 24h at a temperature of 25 ℃.
Repeatedly centrifuging the generated dispersion liquid at 3500rpm, washing the dispersion liquid for multiple times by using deionized water (DI) to neutralize the residual acid until the pH value of the solution supernatant is 6, and collecting the supernatant to obtain the multi-layer MXene nanosheets.
Dispersing the obtained sample in 50mL of deionized water, ultrasonically stripping for 8h in a nitrogen environment, centrifuging and cleaning the dispersion liquid for multiple times at 3500rpm, collecting the obtained supernatant, drying under a vacuum freezing condition and storing.
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)
the Al layer of the MAX phase is stripped through the reaction (1-1), and hydrophilic groups such as-OH, -F and ═ O are attached to the surface of MXene through the reactions (1-2) and (1-3), so that excessive electrons on the surface of the Ti metal are neutralized, and the obtained MXene material has a stable nanosheet structure.
2. Preparation of BiOBr
The BiOBr powder is prepared by a solvothermal method.
Firstly, accurately weighing 2mmol Bi (NO) by using an analytical balance 3 ) 3 ·5H 2 O, which was dispersed in 10mL of ethylene glycol and sonicated at room temperature for 15min as solution A.
② accurately weighing 1mmol CTAB by an analytical balance, dispersing the CTAB in 10mL of glycol, and carrying out ultrasonic treatment at room temperature for 15min to obtain a solution B.
③ the solution B is slowly added into the solution A, and ultrasonic mixing is carried out for 15min at room temperature to disperse evenly.
Fourthly, the mixed solution is magnetically stirred for 30min at room temperature and then poured into a 50mL reaction kettle to react for 12h at 160 ℃.
And fifthly, washing the obtained product respectively with deionized water and absolute ethyl alcohol for 3 times, and drying in a forced air 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.
Precisely weighing 0.1617g Bi (NO) 3 ) 3 ·5H 2 O and 0.0404gNa 2 MoO 6 ·2H 2 O, dispersed in 10mL of ethylene glycolAnd (4) performing ultrasonic treatment at room temperature for 15min to obtain solutions A and B.
② accurately measuring 20mL of the Xene dispersion liquid (0.5mg/L) to be dispersed in 10mL of glycol, and performing ultrasonic treatment at 30 ℃ for 15min to obtain a solution C.
③ accurately weighing a certain amount of BiOBr powder obtained by the previous step, dispersing the BiOBr powder in 10mL of glycol, and carrying out ultrasonic treatment at room temperature for 15min to obtain a solution D.
And fourthly, slowly adding the B, C, D solution into the A solution in turn, and mixing and carrying out ultrasonic treatment for 15min at the temperature of 30 ℃.
Fifthly, the mixed solution is magnetically stirred for 30min at room temperature and then poured into a 100mL reaction kettle to react for 12h at 160 ℃.
Sixthly, washing the obtained product by deionized water and absolute ethyl alcohol respectively for 3 times, and drying the product in a vacuum drying oven at 60 ℃ to obtain BiOBr/Bi 2 MoO 6 @ MXene heterojunction nano material and binary heterojunction Bi without BiOBr 2 MoO 6 @ MXene nano material.
4. Construction of ternary heterojunction photocatalytic composite film
Under normal temperature and pressure, 30mgBiOBr/Bi 2 MoO 6 Dissolving the @ MXene ternary heterojunction powder in 100mL of deionized water, and performing ultrasonic stirring treatment at 30 ℃ for 30min to obtain uniformly dispersed BiOBr/Bi 2 MoO 6 @ MXene precursor solution.
Secondly, slowly pumping and filtering the precursor solution to a PES (polyether sulfone) membrane (with the aperture of 0.22 mu m) under the pressure of 0.1MPa by adopting a vacuum-assisted self-assembly method to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES photocatalysis composite membrane comprises the following components: bi 2 MoO 6 MXene and BiOBr at a mass ratio of 100:10:10, namely M2 film.
Example 2
The preparation method is the same as example 1 except that Bi 2 MoO 6 MXene and BiOBr at a mass ratio of 100:10:20, namely M3 film.
Example 3
The preparation method is the same as example 1 except that Bi 2 MoO 6 The mass ratio of MXene to BiOBr is 100:10:40, namelyFilm No. M4.
Comparative example 1
The preparation method is the same as example 1 except that Bi 2 MoO 6 MXene and BiOBr at a mass ratio of 100:10:0, namely M1 film.
Test example 1
Verification of photocatalytic ability
And evaluating the photocatalytic capacity of the ternary heterojunction photocatalytic film by using a self-made photocatalytic device. The specific method comprises the following steps: firstly, 100mL of deionized water is infiltrated under 0.1MPa by means of a vacuum filtration device, the required time is recorded, and the pure water flux of the membrane is calculated, wherein the effective area of the membrane is 12.56cm 2 . Meanwhile, 100mL of antibiotic solution was permeated by means of a vacuum filtration apparatus and the rejection rate of the membrane was tested. Then, the membrane is taken out of the vacuum filtration device, the membrane is immersed in the penetrating fluid for a photocatalytic degradation experiment, the visible light is continuously irradiated for 8 hours, 5mL of reaction liquid is collected every hour, and finally, the ultraviolet spectrophotometer is used for measuring the absorbance of different antibiotics in characteristic peaks (TC: 356 nm; CIP: 272nm) of the antibiotics to measure the concentration of the antibiotics.
Experimental results show that the ternary heterojunction composite film (M2-M4) achieves better photodegradation effect than the binary heterojunction composite film (M1), and the pure water flux of the photocatalytic film (M4) with the optimal proportion is 1117.13 L.m under the drive of 0.1MPa pressure 2 ·h -1 ·bar -1 The retention rates of TC and CIP are respectively 26.76% and 41.29%, and after the light irradiation is carried out for 8 hours under visible light, the light degradation rates are as high as 92.16% and 90.30%. Compared with a binary heterojunction photocatalytic composite membrane (M1), the pure water flux of M1 is only 438.56L 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 the photocatalytic degradation capability of the membrane and provides a certain reference value for developing a novel ternary heterojunction photocatalytic membrane material.
Test example 2
Contribution of active groups during photodegradation of contaminants
Using Isopropanol (IPA), p-Benzoquinone (BQ) and ethylenediamine tetra-n-ethylDisodium acetate (EDTA-2Na) as active group hydroxyl radical (. OH), superoxide radical (. O) respectively 2 - ) And a cavity (h) + ) The capturing agent of (1). The method is added into a solution containing the antibiotic (TC), and after the solution is irradiated under visible light for 8 hours, the influence of different capture agents on the effect of photodegradation of the antibiotic is calculated. As a result, the TC removal rates were suppressed to some extent, and decreased by 16.04% (. OH) and 39.83% (. O), respectively 2 - ) And 18.93% (h) + ). The results show that the active group O 2 - Plays the most important role in the process of 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. except for etching MAX phase by using LiF + HCl mixed reagent, HF and NH are used by others 4 HF 2 And NaOH and H 2 SO 4 MXene is prepared by etching with the methods, other steps are consistent with the technical scheme of the invention, and the ternary heterojunction photocatalytic composite film can be prepared, so that the aim of the invention is fulfilled.
2. The invention adopts PES membrane as the supporting layer of the composite membrane, if other people adopt organic polymer membrane materials such as Cellulose Acetate (CA) membrane and polyvinylidene fluoride (PVDF) as the supporting layer, other steps (such as Bi) 2 MoO 6 And the preparation of BiOBr, the preparation and mixing proportion of MXene) are consistent with the technical scheme of the invention, and the ternary heterojunction photocatalytic composite membrane can also be prepared, so that the aim of the invention is fulfilled.
3. The invention adopts Bi 2 MoO 6 And BiOBr as a photocatalytic material, if others adopt TiO 2 ，g-C 3 N 4 ZnO and other bismuth-based materials are used as photocatalytic materials, other steps are consistent with the technical scheme of the invention, and the ternary heterojunction photocatalytic composite film can be prepared, so that the purpose of the invention is realized.
4. The invention adopts a hydrothermal method to synthesize the ternary heterojunction nano material in situ, and other steps (Bi) are carried out if other people adopt a direct mixing method 2 MoO 6 Mixing ratio of MXene and BiOBr,The suction filtration stacking method) is consistent with the scheme of the invention, and the ternary heterojunction photocatalytic composite membrane can be prepared, so that the purpose of the invention is realized.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the content of the present specification or other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a ternary heterojunction photocatalytic film comprises the following steps:
(1) preparing a two-dimensional MXene material by chemically etching an MAX phase by using a LiF + HCl mixed solution;
(2) preparing BiOBr powder by a solvothermal method;
(3) preparation of BiOBr/Bi by hydrothermal method 2 MoO 6 @ MXene heterojunction; and
(4) and constructing the ternary heterojunction photocatalytic composite film.
2. The production method according to claim 1, wherein:
the preparation method of the two-dimensional MXene material in the step (1) comprises the following steps:
firstly, 4g LiF is dissolved in 50mL of 12mol/L HCl solution at normal temperature and pressure, and 2.5g Ti is added 3 AlC 2 Magnetically stirring the powder at 25 ℃ for 24 hours to obtain a dispersion liquid;
repeatedly centrifuging the dispersion liquid at 3500rpm, repeatedly washing the dispersion liquid with deionized water, and collecting supernatant to obtain a multilayer MXene nanosheet;
dispersing the multiple layers of MXene nanosheets in 50mL of deionized water, ultrasonically stripping for 8h in a nitrogen environment, centrifuging and cleaning the dispersion liquid for multiple times at 3500rpm, collecting supernatant, and drying under a vacuum freezing condition to obtain a two-dimensional MXene material for storage and later use.
3. The production method according to claim 2, wherein:
and step two, repeatedly washing the solution by the deionized water until the pH value of the supernatant of the solution is 6.
4. The production method according to claim 1, wherein:
the preparation of the BiOBr powder in the step (2) comprises the following steps:
weighing 2mmol of Bi (NO) 3 ) 3 ·5H 2 O, dispersing the solution in 10mL of glycol, and performing ultrasonic treatment at room temperature for 15min to obtain a solution A;
weighing 1mmol of CTAB, dispersing the CTAB in 10mL of glycol, and performing ultrasonic treatment at room temperature for 15min to obtain a solution B;
thirdly, slowly adding the solution B into the solution A, and ultrasonically mixing for 15min at room temperature to obtain a solution C;
fourthly, magnetically stirring the solution C at room temperature for 30min, pouring the solution C into a 50mL reaction kettle, and reacting at 160 ℃ for 12h to obtain a product D;
and fifthly, washing the product D with deionized water and absolute ethyl alcohol respectively for 3 times, and drying in a forced air drying oven at 60 ℃ to obtain BiOBr powder.
5. The production method according to claim 1, wherein:
step (3) of BiOBr/Bi 2 MoO 6 The preparation of the @ MXene heterojunction comprises the following steps:
weighing 0.1617g Bi (NO) 3 ) 3 ·5H 2 O and 0.0404g Na 2 MoO 6 ·2H 2 O, respectively dispersing in 10mL of glycol, and respectively performing ultrasonic treatment at room temperature for 15min to obtain a solution A and a solution B;
measuring 20mL of 0.5mg/L MXene dispersion liquid, dispersing in 10mL of glycol, and performing ultrasonic treatment at 30 ℃ for 15min to obtain a solution C;
③ weighing 40mgBiOBr powder, dispersing in 10mL of glycol, and carrying out ultrasonic treatment for 15min at room temperature to obtain a D solution;
fourthly, slowly adding the B, C, D solution into the A solution in sequence, and mixing and carrying out ultrasonic treatment for 15min at the temperature of 30 ℃ to obtain an E solution;
magnetically stirring the solution E at room temperature for 30min, pouring into a 100mL reaction kettle, and reacting at 160 ℃ for 12h to obtain a product F;
sixthly, washing the product F by deionized water and absolute ethyl alcohol respectively for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain BiOBr/Bi 2 MoO 6 @ MXene heterojunction nano material.
6. The production method according to claim 1, wherein:
the construction of the ternary heterojunction photocatalytic composite film in the step (4) comprises the following steps:
under normal temperature and pressure, 30mgBiOBr/Bi 2 MoO 6 Dissolving the @ 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 @ MXene precursor solution;
② adopting vacuum auxiliary self-assembly method to make BiOBr/Bi under the pressure of 0.1MPa 2 MoO 6 The @ MXene precursor solution is slowly filtered on a PES membrane to construct BiOBr/Bi 2 MoO 6 The @ MXene/PES photocatalysis composite membrane.
7. The production method according to claim 6, wherein:
the pressure is 0.1MPa, and the aperture of the PES membrane is 0.22 mu m.
8. The production method according to claim 6, wherein:
step II of the BiOBr/Bi 2 MoO 6 Bi in @ MXene/PES photocatalytic composite membrane 2 MoO 6 The mass ratio of MXene to BiOBr is 100:10: 40.
9. The ternary heterojunction photocatalytic film prepared by the preparation method of any one of claims 1 to 8.
10. Use of the ternary heterojunction photocatalytic film according to claim 9 in the treatment of antibiotic wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210660174.5A CN115106105B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of ternary heterojunction photocatalytic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210660174.5A CN115106105B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of ternary heterojunction photocatalytic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115106105A true CN115106105A (en) | 2022-09-27 |
| CN115106105B CN115106105B (en) | 2023-10-13 |
Family
ID=83327260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210660174.5A Active CN115106105B (en) | 2022-06-13 | 2022-06-13 | Preparation method and application of ternary heterojunction photocatalytic film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115106105B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115957787A (en) * | 2022-11-23 | 2023-04-14 | 浙江大学 | Preparation method of layered ternary composite photocatalytic material |
| CN117380285A (en) * | 2023-10-09 | 2024-01-12 | 贵州大学 | Z-type heterojunction Bi 2 O 2 CO 3 /UIO-66-NH 2 Composite material, preparation method and application thereof |
| CN117504609A (en) * | 2024-01-05 | 2024-02-06 | 河北建设集团安装工程有限公司 | LED-driven CD S Preparation method and application of photocatalytic film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890654A (en) * | 2017-01-06 | 2017-06-27 | 华南理工大学 | A kind of bismuthyl bromide/bismuth molybdate heterojunction photocatalyst and preparation and application |
| JP2017124365A (en) * | 2016-01-13 | 2017-07-20 | 国立大学法人京都大学 | Water decomposition method under visible light irradiation using silene-aurivillius laminar acid halide as photocatalyst |
| CN111822028A (en) * | 2020-07-21 | 2020-10-27 | 西安工业大学 | Bismuth-based photocatalytic composite film based on MXene and preparation method thereof |
| US20200406233A1 (en) * | 2019-06-25 | 2020-12-31 | Yan'an University | Bismuth oxide/bismuth subcarbonate/bismuth molybdate composite photocatalyst and preparation method thereof |
| CN114177782A (en) * | 2022-01-04 | 2022-03-15 | 成都理工大学 | Photocatalytic MXene composite film and preparation method thereof |
| CN114602552A (en) * | 2022-04-18 | 2022-06-10 | 中国科学院过程工程研究所 | Photocatalytic composite membrane and preparation method and application thereof |
-
2022
- 2022-06-13 CN CN202210660174.5A patent/CN115106105B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017124365A (en) * | 2016-01-13 | 2017-07-20 | 国立大学法人京都大学 | Water decomposition method under visible light irradiation using silene-aurivillius laminar acid halide as photocatalyst |
| CN106890654A (en) * | 2017-01-06 | 2017-06-27 | 华南理工大学 | A kind of bismuthyl bromide/bismuth molybdate heterojunction photocatalyst and preparation and application |
| US20200406233A1 (en) * | 2019-06-25 | 2020-12-31 | Yan'an University | Bismuth oxide/bismuth subcarbonate/bismuth molybdate composite photocatalyst and preparation method thereof |
| CN111822028A (en) * | 2020-07-21 | 2020-10-27 | 西安工业大学 | Bismuth-based photocatalytic composite film based on MXene and preparation method thereof |
| CN114177782A (en) * | 2022-01-04 | 2022-03-15 | 成都理工大学 | Photocatalytic MXene composite film and preparation method thereof |
| CN114602552A (en) * | 2022-04-18 | 2022-06-10 | 中国科学院过程工程研究所 | Photocatalytic composite membrane and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| KUN LIU ET AL.: "Oxygen-functionalized Ti3C2 MXene/exfoliated montmorillonite supported S-scheme BiOBr/Bi2MoO6 heterostructures for efficient photocatalytic quinolone antibiotics degradation", 《CHEMICAL ENGINEERING JOURNAL》, vol. 457, pages 1 - 22 * |
| LINGFU YANG ET AL.: "Construction of 2D/2D/2D BiOBr/(001)-TiO2/Ti3C2Tx heterojunction for enhancing photocatalytic degradation of dye", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 893, pages 2 * |
| ZHAOMEI YANG ET AL.: "Ternary hetero-structured BiOBr/Bi2MoO6@MXene composite membrane: Construction and enhanced removal of antibiotics and dyes from water", 《JOURNAL OF MEMBRANE SCIENCE》, vol. 669, pages 1 - 13 * |
| 张睿宸;杨汉培;高照;柴斯琦;: "MoO_(3-x)/BiOCl异质结光催化剂的制备及其可见光降解盐酸四环素的研究", 环境科技, no. 01 * |
| 杨佳;牛晓君;陈伟仡;安少荣;: "BiOBr@Bi_2MoO_6复合光催化剂制备及其对RhB和BPA降解", 中国环境科学, no. 06 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115957787A (en) * | 2022-11-23 | 2023-04-14 | 浙江大学 | Preparation method of layered ternary composite photocatalytic material |
| CN117380285A (en) * | 2023-10-09 | 2024-01-12 | 贵州大学 | Z-type heterojunction Bi 2 O 2 CO 3 /UIO-66-NH 2 Composite material, preparation method and application thereof |
| CN117380285B (en) * | 2023-10-09 | 2024-06-18 | 贵州大学 | Z-type heterojunction Bi2O2CO3/UIO-66-NH2Composite material, preparation method and application thereof |
| CN117504609A (en) * | 2024-01-05 | 2024-02-06 | 河北建设集团安装工程有限公司 | LED-driven CD S Preparation method and application of photocatalytic film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115106105B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115106105A (en) | Preparation method and application of ternary heterojunction photocatalytic film | |
| Liu et al. | Zeolitic imidazolate framework-based nanomaterials for the capture of heavy metal ions and radionuclides: A review | |
| Cao et al. | Hierarchical nanostructured copper oxide and its application in arsenic removal | |
| CN107233803B (en) | Graphene/silver particle composite filter film and preparation and application thereof | |
| Gan et al. | Achieving high adsorption capacity and ultrafast removal of methylene blue and Pb2+ by graphene-like TiO2@ C | |
| Feng et al. | Synthesis of 2D nanoporous zeolitic imidazolate framework nanosheets for diverse applications | |
| US20120168383A1 (en) | Graphene-iron oxide complex and fabrication method thereof | |
| CN109126893B (en) | Titanium oxycarbide-metal organic framework composite material, and preparation method and application thereof | |
| Yang et al. | Ternary hetero-structured BiOBr/Bi2MoO6@ MXene composite membrane: Construction and enhanced removal of antibiotics and dyes from water | |
| Liu et al. | Electrospun metal–organic framework nanofiber membranes for energy storage and environmental protection | |
| Iqbal et al. | The potential of functionalized graphene-based composites for removing heavy metals and organic pollutants | |
| CN108031433A (en) | A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material | |
| CN109692581B (en) | Two-dimensional layered Ti3C2Membrane, preparation method and application thereof | |
| CN105709610A (en) | Support type ultrathin two-dimensional layered MOF film and preparation method thereof | |
| CN102553523A (en) | Nano zero-valent iron-supported activated carbon fiber, and preparation method and application thereof | |
| CN114177782A (en) | Photocatalytic MXene composite film and preparation method thereof | |
| CN106995531A (en) | The synthesizing preparation method in situ of cellulose/metal organic frame compound and its application | |
| Li et al. | Controlled deposition of Au on (BiO) 2 CO 3 microspheres: the size and content of Au nanoparticles matter | |
| CN114272766B (en) | Two-dimensional MXene-based oil-water separation membrane and preparation method thereof | |
| JP2005263615A (en) | Manganese compound powder carrying manganese oxide, manganese oxide nanoparticle aggregate powder and its manufacturing method, and manganese compound powder carrying metal-adsorbed manganese oxide and metal-adsorbed manganese oxide nanoparticle aggregate powder | |
| CN113764198B (en) | Reduced graphene oxide/MXene porous flexible membrane electrode and preparation method and application thereof | |
| CN106111104B (en) | Sheet zinc silicon layer dihydroxy complex hydroxide photochemical catalyst preparation method and application | |
| Zhao et al. | Sodium alginate intercalated 2D g-C3N4 membrane: Efficient dye removal and photocatalytic self-cleaning | |
| CN105709614A (en) | Ultrathin layered material, and preparation method thereof | |
| CN114262034A (en) | Method for separating rubidium from salt lake brine by using polyvinyl alcohol/chitosan/graphene/nickel copper hexacyanide complex |
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 |