CN113318762A - Preparation method and application of flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod visible-light-driven photocatalyst - Google Patents
Preparation method and application of flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod visible-light-driven photocatalyst Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 79
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002073 nanorod Substances 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 29
- -1 cetyl trimethyl imidazole bromide salt Chemical compound 0.000 claims description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 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 description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims 2
- CZSZEMBKXWDGTG-UHFFFAOYSA-N zinc pentahydrate Chemical compound O.O.O.O.O.[Zn] CZSZEMBKXWDGTG-UHFFFAOYSA-N 0.000 claims 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 abstract description 8
- 229940043267 rhodamine b Drugs 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 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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- B01J35/39—
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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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/396—
-
- B01J35/40—
-
- B01J35/51—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method and application of a flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible-light-induced photocatalyst, wherein a precipitation-ionic liquid method is applied to the preparation of a bismuth oxybromide/zinc oxide composite visible-light-induced photocatalyst, zinc acetate dihydrate is used as a raw material, a glycol/water mixed solution is used as a solvent, formamide is used as a complexing agent, and a hexagonal-prism-shaped zinc oxide nanorod is synthesized by a precipitation method, wherein the edge length of the hexagonal-prism-shaped zinc oxide nanorod is 100-200 nm, and the column length of the hexagonal-prism-shaped zinc oxide nanorod is 0.7-1 mu m; and coating the flower-ball-shaped bismuth oxybromide on a zinc oxide nanorod by adopting an ionic liquid method, and centrifugally washing and drying the compound to obtain the powdery bismuth oxybromide/zinc oxide composite visible-light-driven photocatalyst with excellent visible-light catalytic performance, which can be used for degrading dye rhodamine B by visible-light catalysis. The preparation method is simple, low in cost and easy to operate, and is beneficial to wide application of production practice.
Description
Technical Field
The invention belongs to the technical field of nano visible light catalytic materials and preparation methods thereof, and particularly relates to a preparation method and application of a novel flowerlike bismuth oxybromide-coated zinc oxide nanorod visible light catalyst.
Background
The semiconductor photocatalytic material is widely applied to the fields of environmental pollution treatment and energy conversion, such as pollutant treatment, antibiosis, water decomposition, dye-sensitized solar cells, carbon dioxide removal and the like. Bismuth oxybromide (BiOBr) has a more appropriate band gap (E)gApproximately 2.8eV), no toxicity, better chemical stability and the like, and is a visible light catalytic material with great development potential.
Research proves that BiOBr is mixed with TiO2、C3N4、Bi2S3、ZnFe2O4、Bi2O3、BiOI、AgBr、Bi2MoO6And BiOCl and other semiconductors are compounded, so that the visible light catalytic performance of the bismuth oxybromide can be effectively improved. The activity of a photocatalyst is closely related to its particle size, morphology and internal structure. The bismuth oxybromide with the nano structure is compounded with zinc oxide, so that the light absorption performance of the bismuth oxybromide and the separation efficiency of photo-generated electrons and holes can be more effectively improved. Therefore, the nano-structured bismuth oxybromide/zinc oxide composite photocatalytic material becomes a new research hotspot.
Disclosure of Invention
The invention aims to provide a preparation method and application of a flowered spherical bismuth oxybromide-coated zinc oxide nanorod composite visible-light-driven photocatalyst. The bismuth oxybromide/zinc oxide composite material is prepared by adopting a precipitation-ionic liquid method, and the visible light catalytic performance of the bismuth oxybromide is improved by compounding zinc oxide and controlling the internal structure and morphology of the zinc oxide. The method has the advantages of simple synthesis process, mild preparation conditions, simple operation, low cost and short period, and is beneficial to actual production.
The technical scheme of the invention is as follows:
a flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible light catalyst is a powdery bismuth oxybromide/zinc oxide composite material, zinc oxide is a hexagonal prism-shaped nanorod, the edge length of the hexagonal prism-shaped nanorod is 100-200 nm, the column length of the hexagonal prism-shaped nanorod is 0.7-1 mu m, and flower-ball-shaped bismuth oxybromide is coated on the surface of the zinc oxide. The photocatalyst is prepared by a precipitation-ionic liquid method, zinc acetate dihydrate is dissolved into a glycol/water mixed solvent, formamide complexing agent is added, the pH value of the solution is adjusted by ammonia water, and zinc oxide precipitate is generated after heating; and then, using ethylene glycol methyl ether as a solvent, adding a certain amount of cetyl trimethyl imidazole bromide salt, bismuth nitrate pentahydrate and the synthesized zinc oxide nano rod, reacting at a certain temperature, washing and drying the obtained precipitate to obtain the bismuth oxybromide/zinc oxide composite visible-light-driven photocatalyst.
The preparation method of the flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible-light-driven photocatalyst comprises the following preparation steps: firstly, weighing a certain mass of zinc acetate pentahydrate, fully dissolving the zinc acetate pentahydrate into an ethylene glycol/water mixed solvent through magnetic stirring, adding a formamide complexing agent, uniformly stirring, then dripping ammonia water to adjust the pH value of the solution to 10, and enabling the solution to firstly appear white precipitate and then become a colorless and transparent zinc tetraammine hydroxide solution. Heating the solution at a certain temperature for 30 minutes to obtain white zinc oxide precipitate, respectively centrifugally washing the white zinc oxide precipitate for 3 times by using absolute ethyl alcohol and deionized water, drying the white zinc oxide precipitate at 60 ℃, putting the dried white zinc oxide precipitate into a muffle furnace, and calcining the white zinc oxide precipitate at 450 ℃ for 30 minutes to obtain a hexagonal prism-shaped nano rod with a hexagonal wurtzite structure, wherein the edge length of the zinc oxide is 100-200 nm, and the column length is 0.7-1 mu m; secondly, weighing a certain mass of bismuth nitrate pentahydrate and the prepared zinc oxide to be dispersed in an ethylene glycol monomethyl ether solvent to obtain a mixed solution A, weighing a certain mass of cetyl trimethyl imidazole bromide to be dissolved in the ethylene glycol monomethyl ether solvent to obtain a solution B; slowly dripping the solution B into the mixed solution A, uniformly stirring by magnetic force, transferring the solution B into a 100mL reaction kettle, reacting for 12 hours at 120 ℃ to obtain a light yellow precipitate, centrifugally washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying at 60 ℃ to obtain the bismuth oxybromide/zinc oxide composite visible light photocatalyst.
In the step of preparing the zinc oxide in the technical scheme of the invention, in order to effectively control the appearance and the particle size of the zinc oxide, the volume ratio of the glycol in the glycol/water mixed solvent is 0.05.
In the step of preparing the bismuth oxybromide, the mass percentages of the bismuth nitrate pentahydrate and the cetyl trimethyl imidazole bromide salt in the glycol monomethyl ether solvent are respectively 2.45% and 2.92% in order to control the morphology and the particle size of the bismuth oxybromide.
The flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite photocatalyst prepared by the method is used for degrading organic pollutants by visible light catalysis.
The invention has the advantages that:
1. the invention provides a preparation method of a flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible-light-driven photocatalyst, and the product can efficiently catalyze and degrade organic pollutants under the irradiation of visible light.
2. The invention adopts a precipitation-ionic liquid two-step method to prepare the high-efficiency bismuth oxybromide/zinc oxide composite visible light catalyst, firstly, zinc acetate dihydrate is dissolved into a glycol/water mixed solvent, formamide complexing agent is added, the pH value of the solution is adjusted by ammonia water, and zinc oxide precipitate is generated after heating; then, ethylene glycol methyl ether is used as a solvent, a certain amount of cetyl trimethyl imidazole bromide, bismuth nitrate pentahydrate and the synthesized zinc oxide nano-rod are added, and the reaction is carried out at a certain temperature to obtain the bismuth oxybromide/zinc oxide composite material, so that the aim of improving the visible light catalytic performance of the bismuth oxybromide is fulfilled.
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 micrograph of the zinc oxide nanorods prepared by the method of the present invention.
FIG. 2 is a scanning electron micrograph and an energy spectrum (EDS) of the bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method of the present invention.
FIG. 3 is an X-ray diffraction spectrum of the bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method of the present invention.
FIG. 4 is an ultraviolet-visible absorption spectrum of the bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method of the present invention.
FIG. 5 shows the performance of the bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method of the invention for degrading dye rhodamine B by visible light catalysis.
Detailed Description
The invention adopts a precipitation-ionic liquid method to prepare the flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible light catalyst: firstly weighing a certain mass of zinc acetate pentahydrate, dissolving the zinc acetate pentahydrate into a glycol/water mixed solvent, then adding a certain mass of formamide complexing agent, dripping ammonia water to adjust the pH value of the solution to 10, and uniformly stirring by magnetic force to obtain a colorless and transparent zinc tetraammine hydroxide solution. Heating the solution at 120 ℃ for 30 minutes to obtain white zinc oxide precipitate, centrifugally washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, drying the precipitate at 60 ℃, and then calcining the precipitate in a muffle furnace at 450 ℃ for 30 minutes to obtain the hexagonal prism-shaped nano rod with the hexagonal wurtzite structure, wherein the edge length of the hexagonal prism-shaped nano rod is 100-200 nm, and the column length of the hexagonal prism-shaped nano rod is 0.7-1 mu m. Secondly, weighing a certain mass of bismuth nitrate pentahydrate and the prepared zinc oxide powder, and fully dispersing the bismuth nitrate pentahydrate and the prepared zinc oxide powder into an ethylene glycol monomethyl ether solvent by magnetic stirring to obtain a mixed solution A; weighing a certain mass of cetyl trimethyl imidazole bromide, and fully dissolving the cetyl trimethyl imidazole bromide into an ethylene glycol monomethyl ether solvent through magnetic stirring to obtain a solution B; slowly dripping the solution B into the mixed solution A, uniformly stirring by magnetic force, transferring the solution B into a 100mL reaction kettle, reacting for 12 hours at 120 ℃ to obtain a light yellow precipitate, centrifugally washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying at 60 ℃ to obtain the bismuth oxybromide/zinc oxide composite visible light photocatalyst.
In order to control the appearance and the particle size of the zinc oxide, the volume ratio of the glycol in the glycol/water mixed solvent is 0.05.
In order to control the morphology and the particle size of the bismuth oxybromide, the mass percentages of the bismuth nitrate pentahydrate and the cetyl trimethyl imidazole bromide salt in the ethylene glycol monomethyl ether solvent are respectively 2.45 percent and 2.92 percent.
Example 1
6.585 g (0.03mol) of zinc acetate dihydrate were weighed out and dissolved in 150mL of deionized water, 2.70 g (0.06mol) of formamide was added, magnetic stirring was carried out at room temperature for 10 minutes, and 7.5mL of ethylene glycol was added dropwise to obtain a colorless transparent solution. And (3) dropwise adding ammonia water to adjust the pH value of the solution to 10, firstly generating white turbid matters in the solution, then changing the solution into colorless and transparent zinc tetraammine hydroxide solution, magnetically stirring the solution for 30 minutes, putting the solution into a 100 ℃ oil bath pot, heating the solution for 30 minutes, gradually changing the solution into milky turbid solution, naturally cooling the solution to room temperature, then respectively centrifugally washing precipitates for 3 times by using absolute ethyl alcohol and deionized water, drying the precipitates at 60 ℃, and then putting the precipitates in a muffle furnace to calcine the precipitates for 30 minutes at 450 ℃ to obtain white zinc oxide powder. Secondly, weighing 0.97 g of bismuth nitrate pentahydrate and 0.16 g of the prepared zinc oxide powder, and fully dispersing the bismuth nitrate pentahydrate and the zinc oxide powder into 40mL of glycol monomethyl ether solvent by magnetic stirring to obtain a mixed solution A; weighing 1.16 g of hexadecyl trimethyl imidazole bromide, and fully dissolving into 40mL of ethylene glycol monomethyl ether solvent by magnetic stirring to obtain a solution B; slowly dripping the solution B into the mixed solution A, uniformly stirring by magnetic force, transferring the solution B into a 100mL reaction kettle, reacting for 12 hours at 120 ℃ to obtain light yellow precipitate, respectively centrifugally washing the light yellow precipitate for 3 times by using absolute ethyl alcohol and deionized water, and drying at 60 ℃ to obtain the bismuth oxybromide/zinc oxide composite photocatalyst.
The scanning electron micrograph of the synthesized zinc oxide is shown in FIG. 1. As can be seen from FIG. 1, the zinc oxide is a hexagonal prism-shaped nanorod with a prism length of 100-200 nm and a column length of 0.7-1 μm.
The scanning electron micrograph and the element distribution of the prepared bismuth oxybromide/zinc oxide composite photocatalyst are shown in figure 2. As can be seen from FIG. 2, the flower-ball-shaped bismuth oxybromide is coated on the surface of the zinc oxide, and each element is uniformly distributed in the sample, which indicates that the prepared product is the bismuth oxybromide/zinc oxide composite material.
The X-ray diffraction (XRD) spectrum of the prepared bismuth oxybromide/zinc oxide composite photocatalyst is shown in figure 3. The bismuth oxybromide/zinc oxide composite material only has diffraction peaks of zinc oxide (hexagonal system, JCPDS NO.89-7102) and bismuth oxybromide (tetragonal system, JCPDS NO.09-0393), and has no other impurity peaks.
The ultraviolet-visible absorption spectrum of the bismuth oxybromide/zinc oxide composite photocatalyst is shown in FIG. 4, the light absorption edge of the bismuth oxybromide/zinc oxide composite photocatalyst is about 450nm, and the bismuth oxybromide/zinc oxide composite photocatalyst has strong light absorption in the visible light region (420-550 nm).
Example 2
Evaluation of catalytic performance of flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod visible-light-driven photocatalyst prepared by using method
The bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method degrades dye rhodamine B under the irradiation of visible light. The catalyst dosage is 5 mg, the volume of the rhodamine B aqueous solution is 50ml, and the concentration of the rhodamine B is 10 mg/L. The light source adopts a 500W halogen tungsten lamp, and the optical filter is arranged between the light source and the degradation liquid, so that the incident light is visible light (lambda is more than or equal to 420nm and less than or equal to 800 nm). And (3) measuring the change of the absorbance (concentration) of the rhodamine B by using a UV-3600 type ultraviolet-visible spectrophotometer, taking 5mL of sample every 10 minutes, performing centrifugal separation, and taking supernatant for measurement. FIG. 5 is a graph of rhodamine B degradation by visible light irradiation of the bismuth oxybromide/zinc oxide composite photocatalyst prepared by the method, and it can be seen that rhodamine B can be completely degraded after being irradiated by visible light for 40 minutes under the action of the bismuth oxybromide/zinc oxide composite photocatalyst.
Claims (5)
1. A flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible light catalyst is characterized in that: the zinc oxide is a hexagonal prism-shaped nanorod, the edge length of the nanorod is 100-200 nm, the column length of the nanorod is 0.7-1 mu m, and the flower-ball-shaped bismuth oxybromide is wrapped on the surface of the zinc oxide; the photocatalyst is prepared by a precipitation-ionic liquid method, zinc acetate dihydrate is dissolved into a glycol/water mixed solvent, formamide complexing agent is added, the pH value of the solution is adjusted by ammonia water, and zinc oxide precipitate is generated after heating; and then, by adopting an ionic liquid method, using ethylene glycol monomethyl ether as a solvent, adding a certain amount of cetyl trimethyl imidazole bromide salt, bismuth nitrate pentahydrate and the synthesized zinc oxide nano rod, reacting at a certain temperature, washing and drying the obtained precipitate to obtain the flowerlike-shaped bismuth oxybromide-coated zinc oxide nano rod composite visible light catalyst.
2. A preparation method of a flower-ball-shaped bismuth oxybromide-coated zinc oxide nanorod composite visible-light-driven photocatalyst is characterized by comprising the following preparation steps: firstly, weighing zinc acetate pentahydrate with a certain mass, fully dissolving the zinc acetate pentahydrate in a glycol/water mixed solvent with a certain proportion through magnetic stirring, adding a certain amount of formamide, dropwise adding ammonia water after the magnetic stirring to adjust the pH value of the solution to 10, enabling the solution to firstly appear white precipitate and then become colorless transparent zinc tetraammine hydroxide solution, heating the solution for 30 minutes at a certain temperature, centrifugally washing the obtained precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, drying at 60 ℃ to obtain white powder, and then calcining the white powder in a muffle furnace at 450 ℃ for 30 minutes to obtain a hexagonal prism-shaped zinc oxide nano rod with a hexagonal wurtzite structure, wherein the edge length of the zinc pentahydrate nano rod is 100-200 nm, and the column length of the zinc pentahydrate nano rod is 0.7-1 mu m; secondly, weighing a certain mass of bismuth nitrate pentahydrate and the prepared zinc oxide powder, and fully dissolving the bismuth nitrate pentahydrate and the prepared zinc oxide powder into an ethylene glycol monomethyl ether solvent through magnetic stirring to obtain a mixed solution A; weighing a certain mass of cetyl trimethyl imidazole bromide, and fully dissolving the cetyl trimethyl imidazole bromide into an ethylene glycol monomethyl ether solvent through magnetic stirring to obtain a solution B; slowly dripping the solution B into the mixed solution A, transferring the mixed solution A into a 100mL reaction kettle after magnetic stirring uniformly, reacting for 12 hours at 120 ℃ to obtain a light yellow precipitate, centrifugally washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying at 60 ℃ to obtain the flower-ball-shaped bismuth oxybromide coated zinc oxide nanorod composite visible light photocatalyst.
3. The method for preparing the bismuth oxybromide/zinc oxide composite visible-light-driven photocatalyst according to claim 2, characterized in that: in the step of preparing the zinc oxide, in order to effectively control the appearance and the particle size of the zinc oxide, the volume ratio of the glycol in the glycol/water mixed solvent is 0.05.
4. The method for preparing the bismuth oxybromide/zinc oxide composite visible-light-driven photocatalyst according to claim 2, characterized in that: in the step of preparing the bismuth oxybromide, in order to control the morphology and the particle size of the bismuth oxybromide, the mass percentages of the bismuth nitrate pentahydrate and the cetyl trimethyl imidazole bromide salt in the ethylene glycol monomethyl ether solvent are respectively 2.45 percent and 2.92 percent.
5. Use of the bismuth oxybromide/zinc oxide composite visible light catalyst according to any one of claims 1 to 4 for degrading organic pollutants.
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