CN113289646A - Core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst and preparation method and application thereof - Google Patents
Core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113289646A CN113289646A CN202110487385.9A CN202110487385A CN113289646A CN 113289646 A CN113289646 A CN 113289646A CN 202110487385 A CN202110487385 A CN 202110487385A CN 113289646 A CN113289646 A CN 113289646A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 61
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002057 nanoflower Substances 0.000 title claims description 38
- 239000002105 nanoparticle Substances 0.000 title claims description 35
- 239000002244 precipitate Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 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 claims abstract description 13
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 claims description 8
- 235000013736 caramel Nutrition 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000013379 molasses Nutrition 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- TWDJZUXQDJFLNE-UHFFFAOYSA-N O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] Chemical compound O(Br)Br.[Bi+3].[O-2].[O-2].[Ti+4] TWDJZUXQDJFLNE-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- -1 1-hexadecyl-3-methylimidazole-ammonium bromide Chemical compound 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract 2
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- OLBRKKJBIBPJSE-UHFFFAOYSA-N bismuth;bromo hypobromite Chemical group [Bi].BrOBr OLBRKKJBIBPJSE-UHFFFAOYSA-N 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J35/23—
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- B01J35/39—
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- B01J35/397—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a micron core-shell structure titanium dioxide-bismuth oxybromide visible-light-induced photocatalyst, and a preparation method and application thereof. The invention adopts an ionic liquid-hydrothermal two-step method to prepare titanium dioxide-bismuth oxybromide with a nano core-shell structure, wherein the diameter of a bismuth oxybromide core is 250nm, and the thickness of a bismuth tungstate shell is 30-50 nm. The invention applies an ionic liquid-hydrothermal two-step method, uses 2-methoxy ethanol as a solvent, and firstly uses bismuth nitrate pentahydrate and 1-hexadecyl-3-methylimidazole-ammonium bromide to react to generate the nano bismuth oxybromide microspheres. And adding titanium sulfate and glucose, loading titanium dioxide on the surface of the bismuth oxybromide microsphere to obtain a titanium dioxide-bismuth oxybromide precipitate, washing and drying the precipitate to obtain the titanium dioxide-bismuth oxybromide visible light catalyst with the nano core-shell structure, wherein the titanium dioxide-bismuth oxybromide visible light catalyst can be used for degrading organic pollutants under the condition of visible light. The preparation method is simple, easy to operate and beneficial to wide application of production practice.
Description
Technical Field
The invention belongs to the technical field of nano materials and visible light catalytic materials and preparation methods thereof, and particularly relates to a nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst with a core-shell structure, and a preparation method and application thereof.
Background
The semiconductor photocatalytic material is widely applied to the fields of environmental pollution treatment and energy conversion, such as pollutant degradation, hydrogen production, corrosion prevention, dye-sensitized solar cells and the like. The intrinsic forbidden band width of the titanium dioxide semiconductor is about 3.2eV, so the maximum wavelength of excited electrons for jumping from a valence band to a conduction band is 387.5nm, namely, the electrons can only be excited by ultraviolet light, and the utilization of the titanium dioxide to sunlight is greatly influenced.
The study shows that g-C3N4、ZnO、Fe3O4、Bi2O3The semiconductor such as BiOI, AgBr, BiOCl and the like is compounded with titanium dioxide, so that the band gap of the semiconductor can be reduced, the composite materials can be excited by visible light, and the aim of enhancing the visible light catalytic performance of the composite materials is fulfilled. The core/shell composite structure of the nanoflower/nanoparticle is beneficial to the light absorption performance of the photocatalytic material, the migration of carriers and the separation of photo-generated electron-hole pairs, and the bismuth oxybromide/titanium dioxide heterojunction material can more effectively improve the migration of titanium dioxide photo-generated carriers under the action of an internal electric field. Therefore, the core/shell structure nanoflower/nano-particle bismuth oxybromide/titanium dioxide photocatalytic material becomes a new research hotspot.
Disclosure of Invention
The invention aims to provide a nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst with a core-shell structure, and a preparation method and application thereof. The invention applies the ionic liquid-hydrothermal two-step method to the preparation of the bismuth oxybromide/titanium dioxide composite material to control the internal structure and the morphology, thereby improving the visible light catalytic performance of the titanium dioxide. The preparation equipment is simple, the synthesis condition is mild, the operation is simple, the period is short, and the method is favorable for actual production.
The technical scheme of the invention is as follows:
a nano flower/nano particle bismuth oxybromide/titanium dioxide efficient visible light catalyst with a core-shell structure is a powdery product, wherein the diameter of the bismuth oxybromide (core) is about 250nm, and the diameter of the titanium dioxide (shell) is 30-50nm, and the nano flower/nano particle bismuth oxybromide/titanium dioxide efficient visible light catalyst is prepared by an ionic liquid-hydrothermal two-step method. The preparation method is that 2-methoxy ethanol is used as solvent, bismuth nitrate pentahydrate and ionic liquid 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C ]16Mim]Br) to generate the bismuth oxybromide three-dimensional nanoflower. And adding titanium sulfate and glucose, loading titanium dioxide nanoparticles on the surface of the bismuth oxybromide nanoflower to obtain bismuth oxybromide/titanium dioxide precipitate, washing and drying the precipitate to obtain the core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst.
The preparation method of the core-shell structured nano flower/nano particle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst comprises the following steps: firstly, weighing a certain mass of bismuth nitrate pentahydrate, and fully dissolving the bismuth nitrate pentahydrate in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution A; weighing a certain mass of ionic liquid 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C ]16Mim]Br) and fully dissolving the mixture in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution B; and (4) dripping the solution A into the solution B, and uniformly stirring by magnetic force. Reacting the mixed solution at 120 ℃ for 12 hours to obtain a light yellow precipitate, centrifugally washing the precipitate for 3 times by using deionized water, and freeze-drying to obtain light yellow bismuth oxybromide powder; secondly, titanium sulfate, glucose, the synthesized bismuth oxybromide powder and deionized water with certain mass are fully mixed by magnetic stirring, and react for 12 hours at 180 ℃ to obtain yellow-white precipitate, and the precipitate is usedAnd centrifugally washing with deionized water for 3 times, and freeze-drying to obtain the nano flower/nano particle bismuth oxybromide/titanium dioxide visible light catalyst with a core-shell structure, wherein the diameter of the bismuth oxybromide nano flower (core) is about 250nm, and the diameter of the titanium dioxide particle (shell) is 30-50 nm.
In the technical scheme of the invention, in the step of preparing the titanium dioxide (shell), in order to control the size of titanium dioxide particles (shell), the molar ratio of the titanium sulfate to the bismuth nitrate pentahydrate is 4: 1.
the nano flower/nano particle bismuth oxybromide-titanium dioxide visible light catalyst with the core-shell structure prepared by the method is used for degrading caramel pigment in molasses wastewater under the condition of visible light.
The invention has the advantages that:
1. the invention provides a preparation method of a nanoflower/nanoparticle bismuth oxybromide/titanium dioxide efficient visible-light-driven photocatalyst with a core-shell structure, which can be used for efficiently photocatalytic degradation of caramel pigment in molasses wastewater under the irradiation of visible light.
2. The invention adopts a two-step solvothermal method to prepare the nano flower/nano particle bismuth oxybromide/titanium dioxide efficient visible light catalyst with a core-shell structure, uses 2-methoxyethanol as a solvent, and uses bismuth nitrate pentahydrate and ionic liquid 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C)16Mim]Br) to obtain the three-dimensional nano flower bismuth oxybromide. And adding titanium sulfate and glucose, loading titanium dioxide nanoparticles on the surface of the bismuth oxybromide to obtain bismuth oxybromide/titanium dioxide precipitate, washing and drying the precipitate to obtain the nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-induced photocatalyst with the core-shell structure.
The preparation method is simple, easy to operate and beneficial to wide application of production practice.
The room temperature in the present invention means a temperature of 25 to 35 ℃.
Drawings
FIG. 1 is a scanning electron microscope picture of the core-shell structured nano flower/nano particle bismuth oxybromide/titanium dioxide photocatalyst prepared by the method of the present invention.
FIG. 2 is a high-resolution transmission electron micrograph of the core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide photocatalyst prepared by the method of the present invention.
FIG. 3 is an X-ray diffraction diagram of the core-shell structured nano-flower/nano-particle bismuth oxybromide/titanium dioxide photocatalyst prepared by the method of the present invention.
FIG. 4 is a UV-VISIBLE absorption spectrum of the core-shell structured nano-flower/nano-particle bismuth oxybromide/titanium dioxide photocatalyst prepared by the method of the present invention.
FIG. 5 shows the photocatalytic degradation of caramel pigment in molasses wastewater by the nano flower/nano particle bismuth oxybromide/titanium dioxide photocatalyst with core-shell structure prepared by the method of the invention under the irradiation of visible light.
Detailed Description
The preparation of the core-shell structured nano flower/nano particle bismuth oxybromide/titanium dioxide visible-light-induced photocatalyst comprises the following steps: firstly, weighing a certain mass of bismuth nitrate pentahydrate, and fully dissolving the bismuth nitrate pentahydrate in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution A; weighing a certain mass of ionic liquid 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C ]16Mim]Br) and fully dissolving the mixture in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution B; and (4) dripping the solution A into the solution B, and uniformly stirring by magnetic force. Reacting the mixed solution at 120 ℃ for 12 hours to obtain a light yellow bismuth oxybromide precipitate, centrifugally washing the precipitate for 3 times by using deionized water, and freeze-drying to obtain light yellow bismuth oxybromide powder; secondly, titanium sulfate, glucose, the synthesized bismuth oxybromide powder and deionized water with certain mass are fully mixed through magnetic stirring, the mixture reacts for 12 hours at 180 ℃ to obtain yellow-white precipitate, the precipitate is centrifugally washed for 3 times by the deionized water, and the nano flower/nano particle bismuth oxybromide/titanium dioxide visible light catalyst with the core-shell structure is obtained after freeze drying.
To control the size of the titanium dioxide particles (shells), the molar ratio of titanium sulfate to bismuth nitrate pentahydrate was 4: 1.
the core-shell structured bismuth oxybromide/titanium dioxide photocatalyst prepared by the method of the present invention and the application thereof will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Firstly, weighing 0.97 g of bismuth nitrate pentahydrate, and fully dissolving the bismuth nitrate pentahydrate in 40 ml of 2-methoxyethanol solvent by magnetic stirring to obtain a solution A; 1.16 g of 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C ] was weighed16Mim]Br) and fully dissolved into 40 ml of 2-methoxy ethanol solvent by magnetic stirring to obtain solution B; and (3) dripping the solution A into the solution B, and uniformly mixing by magnetic stirring. Reacting the mixed solution at 120 ℃ for 12 hours to obtain a light yellow bismuth oxybromide precipitate, centrifugally washing the precipitate with deionized water for 3 times, and freeze-drying to obtain light yellow bismuth oxybromide powder; secondly, a certain amount of titanium sulfate, glucose, the synthesized bismuth oxybromide powder and deionized water are fully mixed through magnetic stirring, the mixture reacts for 12 hours at 180 ℃ to obtain a yellow-white precipitate, the precipitate is centrifugally washed for 3 times by the deionized water, and the precipitate is freeze-dried to obtain the core-shell structured nano flower/nano particle bismuth oxybromide/titanium dioxide visible light catalyst.
The scanning electron microscope and high resolution transmission electron microscope photographs of the bismuth oxybromide/titanium dioxide with the core-shell structure are shown in fig. 1 and fig. 2. As can be seen from FIGS. 1 and 2, the powder is core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide, wherein the diameter of the bismuth oxybromide nanoflower (core) is 250nm, and the diameter of the titanium dioxide nanoparticle (shell) is 30-50 nm.
The XRD pattern of the synthesized bismuth oxybromide/titanium dioxide with the core-shell structure is shown in figure 3. FIG. 3 shows that the diffraction peaks of bismuth oxybromide/titania correspond to the tetragonal bismuth oxybromide standard card (JCPDS09-0393) and the standard card of anatase titania (JCPDS21-1272), with no hetero-peaks of the other phases. The diffraction peak intensities of the (110) crystal face and the titanium dioxide (101) crystal face of the bismuth oxybromide are higher, and the diffraction peaks of the other crystal faces are wider and lower in intensity, so that the bismuth oxybromide and the titanium dioxide respectively grow directionally along the (110) crystal face and the (101) crystal face, and the bismuth oxybromide/titanium dioxide synthesized by the method has higher crystallinity and purity and no other impurity phases.
The ultraviolet-visible absorption spectrum of the bismuth oxybromide/titanium dioxide is shown in FIG. 4, the absorption edge is near 420nm, and the absorption is strong in the visible wavelength range of 420-700 nm.
Example 2
Evaluation of catalytic performance of core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst prepared by using method
The nanometer flower/nanometer particle bismuth oxybromide/titanium dioxide catalyst with the core-shell structure prepared by the method degrades caramel pigment in molasses wastewater under the irradiation of visible light, the adding amount of the catalyst is 25 mg, the concentration of the caramel pigment is 200 mg/L, the volume is 50 ml, a 300W halogen tungsten lamp is adopted as a light source, an optical filter is arranged between the light source and degradation liquid, incident light is visible light (lambda is more than or equal to 420nm and less than or equal to 800nm), and the change of absorbance (concentration) of rhodamine B is measured by adopting an UV-3600 type ultraviolet-visible spectrophotometer. 5mL of sample is taken every 1 hour, after centrifugal separation, the supernatant is taken for absorbance measurement of rhodamine B. FIG. 5 is a curve of photocatalytic degradation of caramel pigment under visible light irradiation by the nano flower/nano particle bismuth oxybromide/titanium dioxide catalyst with the core-shell structure prepared by the method of the present invention. From FIG. 5, it can be seen that under the action of the bismuth oxybromide/titanium dioxide photocatalyst, the degradation rate of the caramel pigment reaches 73% after 12 hours of visible light irradiation.
Claims (4)
1. A nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst with a core-shell structure is characterized in that: the bismuth oxybromide nano flower/titanium dioxide powder is prepared by applying an ionic liquid-hydrothermal two-step method, wherein the diameter of a bismuth oxybromide nano flower (core) is about 250nm, and the diameter of a titanium dioxide nano particle (shell) is 30-50 nm.
2. A preparation method of a core-shell structured bismuth oxybromide/titanium dioxide nanoflower/nanoparticle visible-light-induced photocatalyst is characterized by comprising the following preparation steps: firstly, weighing a certain mass of bismuth nitrate pentahydrate, and fully dissolving the bismuth nitrate pentahydrate in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution A; weighing a certain mass of ionic liquid 1-hexadecyl-3-methylimidazole-ammonium bromide ([ C ]16Mim]Br) and fully dissolving the mixture in a 2-methoxy ethanol solvent by magnetic stirring to obtain a solution B; dropping the solution A into the solution BIn the middle, magnetic stirring is carried out uniformly; pouring the mixed solution into a reaction kettle, reacting for 12 hours at 120 ℃ to obtain light yellow precipitate, centrifugally washing the light yellow precipitate for 3 times by using deionized water, and freeze-drying to obtain light yellow bismuth oxybromide powder; secondly, titanium sulfate, glucose, synthesized bismuth oxybromide powder and deionized water with certain mass are fully mixed through magnetic stirring, poured into a reaction kettle to react for 12 hours at 180 ℃ to obtain yellow-white precipitate, the yellow-white precipitate is washed for 3 times by the deionized water and is frozen and dried to obtain the core-shell structure bismuth oxybromide/titanium dioxide nanoflower/nanoparticle visible light catalyst, wherein the diameter of the bismuth oxybromide (core) is about 250nm, and the diameter of the titanium dioxide (shell) is 30-50 nm.
3. The preparation method of the core-shell structured bismuth oxybromide/titanium dioxide nanoflower/nanoparticle according to claim 2, wherein the preparation method comprises the following steps: in the step of preparing the titanium dioxide shell, in order to control the granularity of the titanium dioxide (shell), the molar ratio of the titanium sulfate to the bismuth oxybromide is 4: 1.
4. use of the bismuth oxybromide/titanium dioxide nanoflower/nanoparticle catalyst with the core-shell structure as claimed in any one of claims 1 to 4 for catalytically degrading caramel pigment in molasses wastewater under visible light conditions.
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