CN112169813A - Preparation method and application of bismuth oxyiodide/bismuth oxybromide composite photocatalyst - Google Patents
Preparation method and application of bismuth oxyiodide/bismuth oxybromide composite photocatalyst Download PDFInfo
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- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 29
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012153 distilled water Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 23
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940093930 potassium iodate Drugs 0.000 claims abstract description 10
- 235000006666 potassium iodate Nutrition 0.000 claims abstract description 10
- 239000001230 potassium iodate Substances 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 230000015556 catabolic process Effects 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 13
- 229940107698 malachite green Drugs 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002835 absorbance Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- -1 bismuth oxyiodide iodate Chemical compound 0.000 description 5
- 239000012535 impurity Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
A preparation method and application of a bismuth oxyiodide/bismuth oxybromide composite photocatalyst belong to the field of photocatalytic semiconductor materials. Firstly, dissolving bismuth nitrate in distilled water, dissolving potassium iodate in the solution, transferring the obtained suspension into a reaction kettle, reacting for 5-8 hours at 130-150 ℃, naturally cooling to room temperature, washing, drying and drying the obtained product to obtain bismuth oxyiodate. And then dissolving bismuth nitrate and hexadecyl trimethyl ammonium bromide in distilled water, transferring the obtained suspension into a reaction kettle, reacting for 18-24 hours at 140-160 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide. And finally, respectively adding bismuth oxyiodide and bismuth oxybromide into ethanol, dropwise adding a bismuth oxyiodide solution into a bismuth oxybromide solution after ultrasonic treatment, continuing ultrasonic treatment, dropwise adding acetone into the mixed solution, magnetically stirring, precipitating, and drying to obtain the composite photocatalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalytic semiconductor materials, and relates to a BiOIO3A preparation method of a composite photocatalyst.
Background
The photocatalysis technology is a novel environment-friendly technology. The photocatalysis technology can generate high efficiency at room temperature, can utilize sunlight, and is an energy-saving pollutant treatment technology with wide application prospect. Photocatalyst must be of great concern if the function of the photocatalytic technology is to be effectively exerted, and is the key to the photocatalytic technology.
Bismuth oxyiodate (BiOIO)3) TiO as a novel bismuth-based photocatalyst and common catalyst2(P25) exhibits superior photocatalytic performance compared to other photocatalytic materials. BiOIO3The excellent photocatalytic activity is caused by the layered structure and the internal polar property, the layered structure and the internal polar property both facilitate the separation of photo-generated electron-hole pairs, and the high valence band potential indicates that the holes have strong oxidizability and can generate strong oxidation free radicals, and the characteristics are very beneficial to the degradation of pollutants.
But due to BiOIO3The forbidden band width is large, and the response capability to visible light is limited, so the visible light photocatalytic activity of the photocatalyst is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a bismuth oxyiodate composite photocatalyst, which overcomes the defects in the prior art. By constructing a heterostructure of bismuth oxyiodide and bismuth oxybromide, photoinduced electrons and holes can be effectively separated, so that the photo-corrosion of the bismuth oxyiodide is reduced, the photocatalytic performance is improved, and the degradation effect of the composite catalyst in the aspect of sewage treatment is improved.
In order to achieve the above purpose, the invention provides the following technical scheme;
a preparation method of a bismuth oxyiodide/bismuth oxybromide composite photocatalyst comprises the following steps:
step 1, preparation of bismuth oxyiodate: dissolving bismuth nitrate in distilled water, dissolving potassium iodate in the solution after the bismuth nitrate is completely dissolved, continuously stirring for 10-30 minutes, transferring the obtained suspension into a reaction kettle, reacting for 5-8 hours at 130-150 ℃, naturally cooling to room temperature, washing, drying and drying the obtained product to obtain bismuth oxyiodate.
Step 2, preparing bismuth oxybromide: dissolving bismuth nitrate and hexadecyl trimethyl ammonium bromide in distilled water, stirring for 1-2h, transferring the obtained suspension into a reaction kettle, reacting for 18-24 h at 140-160 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain bismuth oxybromide.
Step 3, preparing the bismuth oxyiodide/bismuth oxybromide composite photocatalyst: respectively adding bismuth oxyiodide and bismuth oxybromide into ethanol, carrying out ultrasonic treatment for 1-2h, dropwise adding a bismuth oxyiodide solution into a bismuth oxybromide solution after the ultrasonic treatment is finished, continuously carrying out ultrasonic treatment on the mixed solution for 2-3 h, dropwise adding acetone into the mixed solution, carrying out magnetic stirring for 24h, precipitating, and drying at 60 ℃ for 12h to obtain the composite photocatalyst.
Further, the molar mass ratio of the bismuth nitrate to the potassium iodate in the step 1 is 1: 1;
further, the mass ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide in the step 2 is 1: 1;
further, in the step 3, the mass ratio of bismuth oxyiodide iodate to bismuth oxybromide is 1: 1-1.4;
further, bismuth oxyiodide iodate and bismuth oxybromide are respectively added into ethanol in the step 3, and the solid-liquid volume ratio of the bismuth oxyiodide iodate or the bismuth oxybromide to the ethanol is 1: 150-200.
Further, after the acetone is added in the step 3 in a dropwise manner, the volume fraction of the acetone in the final mixed solution is 40-60%.
The bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared by the method can be used for photocatalytic degradation of printing and dyeing wastewater, and the specific method comprises the following steps:
(1) weighing a certain amount of bismuth oxyiodide/bismuth oxybromide photocatalyst, and adding the photocatalyst into a colorimetric tube;
(2) preparing 20mg/L malachite green solution, weighing 50ml, and adding into a colorimetric tube;
(3) and putting the colorimetric tube into a photocatalytic reactor, and stirring for 30min under the dark condition to ensure that the system achieves absorption/desorption balance. Then turning on a light source, sampling 3ml of mixed solution every 30min under magnetic stirring, centrifuging, taking supernatant, and filtering by using a needle filter to obtain clarified liquid;
(4) and measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer to calculate the degradation rate.
The invention has the beneficial effects that:
1) the raw materials used by the invention are bismuth nitrate, potassium iodate, hexadecyl trimethyl ammonium bromide and the like which are all cheap and easily available, the experimental method is simple and feasible, the operation is simple and convenient, and the cost is greatly reduced.
2) The composite photocatalyst with visible light response can be used for removing organic matters in printing and dyeing wastewater, and has important significance for environmental management.
3) The composite photocatalyst prepared by the invention has high purity and good repeatability.
4) The ultrasonic impregnation method adopted by the invention has good controllability and mild conditions. BiOIO3Is an n-type semiconductor with Fermi level very close to its conduction band, BiOBr is a p-type semiconductor with Fermi level close to its valence band, constructing p-n type heterojunction structure is a very effective method for separating photo-generated electrons-holes, and BiOIO is favorable for photocatalytic reaction due to internal electric field3The energy level of the BiOBr and the BiOBr are well matched with an overlapped energy band structure, so that p-n type BiOIO with improved photocatalytic performance is expected to be prepared3a/BiOBr heterostructure.
5) The composite material is prepared by a 3-step method, XRD images show that the bismuth oxyiodide and the bismuth oxybromide with very high purity are prepared in the steps 1 and 2, no impurities are generated, diffraction peaks of the composite material synthesized in the step 3 are clear and well matched, the material is proved to have high crystallinity and a two-phase structure without impurities, and a degradation curve chart also proves that the composite phase catalyst has a better catalytic effect than a single-phase catalyst.
Drawings
FIG. 1 is an XRD spectrum of a photocatalyst prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2;
FIG. 2 is a graph showing degradation curves of photocatalysts obtained in examples 1 to 3 of the present invention and comparative examples 1 to 2 for MG;
FIG. 3 is a graph showing the degradation kinetics of the photocatalyst for MG obtained in examples 1 to 3 of the present invention and comparative examples 1 to 2;
FIG. 4 is an SEM image of a bismuth oxyiodate/bismuth oxybromide composite photocatalytic material prepared in example 2 of the present invention;
Detailed Description
The invention will be further described with reference to the drawings, which are illustrative embodiments and illustrative of the invention herein for the purpose of illustrating the invention and are not to be construed as limiting the invention. Further, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Step 1, dissolving 0.485g of bismuth nitrate in 80ml of distilled water, adding 0.214g of potassium iodate after the bismuth nitrate is completely dissolved, stirring for 10 minutes, transferring the obtained suspension into a 100ml reaction kettle, keeping the suspension at 150 ℃ for 5 hours, naturally cooling the suspension at room temperature, alternately washing the suspension with distilled water and absolute ethyl alcohol, and drying the washing solution to obtain bismuth oxyiodate.
And 2, dissolving 1g of bismuth nitrate and 1g of hexadecyl trimethyl ammonium bromide in 50ml of distilled water, stirring for 1h, transferring the obtained suspension into a 100ml reaction kettle, reacting for 18h at 160 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide.
And 3, respectively adding 0.1g of bismuth oxyiodide iodate and 0.1g of bismuth oxybromide into 20ml of ethanol, carrying out ultrasonic treatment for 1h, pouring the bismuth oxyiodate solution into the bismuth oxybromide solution after the ultrasonic treatment is finished, continuing the ultrasonic treatment for 2h on the mixed solution, then dropwise adding 20ml of acetone into the mixed solution by using a rubber head dropper, carrying out magnetic stirring for 24h, carrying out precipitation, and drying at 60 ℃ for 12h to obtain the composite catalyst in which the mass ratio of the bismuth oxyiodate to the bismuth oxybromide is 1:1.
Example 2
Step 1, dissolving 0.485g of bismuth nitrate in 80ml of distilled water, adding 0.214g of potassium iodate after the bismuth nitrate is completely dissolved, stirring for 10 minutes, transferring the obtained suspension into a 100ml reaction kettle, keeping the suspension at 150 ℃ for 5 hours, naturally cooling the suspension at room temperature, alternately washing the suspension with distilled water and absolute ethyl alcohol, and drying the washing solution to obtain bismuth oxyiodate.
And 2, dissolving 1g of bismuth nitrate and 1g of hexadecyl trimethyl ammonium bromide in 50ml of distilled water, stirring for 2 hours, transferring the obtained suspension into a 100ml reaction kettle, reacting for 24 hours at 140 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide.
And 3, respectively adding 0.1g of bismuth oxyiodide and 0.12g of bismuth oxybromide into 20ml of ethanol, carrying out ultrasonic treatment for 1h, pouring the bismuth oxyiodide solution into the bismuth oxybromide solution after the ultrasonic treatment is finished, continuing the ultrasonic treatment for 2h on the mixed solution, then dropwise adding 20ml of acetone into the mixed solution by using a rubber head dropper, carrying out magnetic stirring for 24h, carrying out precipitation, and drying at 60 ℃ for 12h to obtain the composite catalyst, wherein the mass ratio of the bismuth oxyiodide to the bismuth oxybromide is 1: 1.2.
Example 3
Step 1, dissolving 0.485g of bismuth nitrate in 80ml of distilled water, adding 0.214g of potassium iodate after the bismuth nitrate is completely dissolved, stirring for 10 minutes, transferring the obtained suspension into a 100ml reaction kettle, keeping the temperature at 130 ℃ for 8 hours, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain bismuth oxyiodate.
And 2, dissolving 1g of bismuth nitrate and 1g of hexadecyl trimethyl ammonium bromide in 50ml of distilled water, stirring for 2 hours, transferring the obtained suspension into a 100ml reaction kettle, reacting for 24 hours at 140 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide.
And 3, respectively adding 0.1g of bismuth oxyiodide and 0.14g of bismuth oxybromide into 20ml of ethanol, carrying out ultrasonic treatment for 1h, pouring the bismuth oxyiodide solution into the bismuth oxybromide solution after the ultrasonic treatment is finished, continuing the ultrasonic treatment for 2h on the mixed solution, then dropwise adding 20ml of acetone into the mixed solution by using a rubber head dropper, carrying out magnetic stirring for 24h, carrying out precipitation, and drying at 60 ℃ for 12h to obtain the composite catalyst, wherein the mass ratio of the bismuth oxyiodide to the bismuth oxybromide is 1: 1.4.
And (3) performance determination of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst:
the crystalline phase structure of the bismuth oxyiodide/bismuth oxybromide composite visible-light-driven photocatalyst prepared in the examples 1 to 3 is analyzed by a Japanese-science D/max2500PC autorotation X-ray diffractometer, wherein X-rays are Cu target Ka voltage 40kV, current 100mA, step length is 0.02 degrees, and scanning range is 5-80 degrees. The X-ray diffraction pattern is shown in figure 1, the diffraction peak is basically consistent with that of a standard card (PDF #26-2019), and no diffraction peak with any miscellaneous peak appears, which indicates that the obtained sample is bismuth oxyiodate; the well-matched strong diffraction peaks of the composite demonstrate that the sample is a two-phase structure free of other impurities and has high crystallinity.
Comparative example 1
Dissolving 0.485g of bismuth nitrate in 80ml of distilled water, adding 0.214g of potassium iodate after the bismuth nitrate is completely dissolved, stirring for 10 minutes, transferring the obtained suspension into a 100ml reaction kettle, keeping the suspension at 150 ℃ for 5 hours, naturally cooling the suspension at room temperature, alternately washing the suspension with distilled water and absolute ethyl alcohol, and drying the washing solution to obtain bismuth oxyiodate.
Comparative example 2
Dissolving 1g of bismuth nitrate and 1g of hexadecyl trimethyl ammonium bromide in 50ml of distilled water, stirring for 2 hours, transferring the obtained suspension into a 100ml reaction kettle, reacting for 24 hours at 140 ℃, naturally cooling at room temperature, alternately washing with distilled water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide.
Comparative example 3
0.1g of bismuth oxyiodate is weighed and dissolved in 60mL of ethanol, ultrasonic dispersion is carried out, bismuth nitrate and hexadecyl trimethyl ammonium bromide are added to form uniform mixed solution, and then the solution is transferred into a 100mL reaction kettle and undergoes hydrothermal reaction for 24 hours at 180 ℃. Cooling to room temperature, alternately washing with deionized water and ethanol, and drying at 60 deg.C. The molar mass ratio of bismuth oxyiodide to bismuth oxybromide in the prepared bismuth oxyiodate/bismuth oxybromide composite material is 1:1.
Application example 1
The method comprises the following steps: weighing 30mg of the bismuth oxyiodide/bismuth oxybromide photocatalyst prepared in the example 1, and adding the weighed sample into a colorimetric cylinder;
step two: preparing 20mg/L malachite green solution, measuring 50ml, and adding into a colorimetric tube;
step three: and (3) placing the colorimetric tube into a photocatalytic reactor, and stirring for 30min under a dark condition to ensure that the system achieves absorption/desorption balance. Then turning on a light source, sampling 3ml of mixed solution every 30min under magnetic stirring, centrifuging for 3 min, taking supernatant, and filtering by using a needle filter to obtain clarified liquid;
step four: measuring the absorbance of the solution by using a UV759 ultraviolet-visible spectrophotometer, and calculating the degradation rate;
the degradation effect of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 1 is shown in fig. 2, after the reaction is carried out for 120min, the degradation rate of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 1 to malachite green is 86.61%, and the composite catalyst has high photocatalytic activity.
Application example 2
Step two: weighing 30mg of the bismuth oxyiodide/bismuth oxybromide photocatalyst prepared in the example 2, and adding the weighed sample into a colorimetric cylinder;
the other steps are the same as in example 1.
The degradation effect of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 2 is shown in fig. 2, wherein after the reaction is carried out for 120min, the degradation rate of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 2 on malachite green is 97.37%, and the composite catalyst has high photocatalytic activity.
Application example 3
Step two: weighing 30mg of the bismuth oxyiodide/bismuth oxybromide photocatalyst prepared in the example 3, and adding the weighed sample into a colorimetric cylinder;
the other steps are the same as in example 1.
The degradation effect of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 3 is shown in fig. 2, wherein after the reaction is carried out for 120min, the degradation rate of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst prepared in example 3 on malachite green is 92.38%, and the composite catalyst has high photocatalytic activity.
Comparative application example 1
Step two: weighing 30mg of bismuth oxyiodate prepared in comparative example 1, and adding the bismuth oxyiodate into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of bismuth oxybromide prepared in comparative example 1 is shown in fig. 2, and the degradation rate of bismuth oxyiodate to malachite green after 120min of reaction is 47.49%.
Comparative application example 2
Step two: weighing 30mg of bismuth oxybromide prepared in comparative example 2, and adding the weighed bismuth oxybromide into a colorimetric cylinder filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of the bismuth oxybromide prepared in comparative example 2 is shown in fig. 2, and after the reaction time of 120min, the degradation rate of the bismuth oxybromide to malachite green is 18.36%.
Comparative application example 3
Step two: weighing 30mg of bismuth oxyiodide/bismuth oxybromide prepared in comparative example 3, and adding the weighed material into a colorimetric cylinder filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation rate of the bismuth oxyiodate/bismuth oxybromide compound prepared in comparative example 3 on malachite green was 79.42%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. A preparation method of a bismuth oxyiodide/bismuth oxybromide composite photocatalyst is characterized by comprising the following steps:
step 1, preparation of bismuth oxyiodate: dissolving bismuth nitrate in distilled water, dissolving potassium iodate in the solution after the bismuth nitrate is completely dissolved, continuously stirring for 10-30 minutes, transferring the obtained suspension into a reaction kettle, reacting for 5-8 hours at 130-150 ℃, naturally cooling to room temperature, washing, drying and drying the obtained product to obtain bismuth oxyiodide;
step 2, preparing bismuth oxybromide: dissolving bismuth nitrate and hexadecyl trimethyl ammonium bromide in distilled water, stirring for 1-2 hours, transferring the obtained suspension into a reaction kettle, reacting for 18-24 hours at 140-160 ℃, naturally cooling at room temperature, alternately washing distilled water and absolute ethyl alcohol, and drying to obtain bismuth oxybromide;
step 3, preparing the bismuth oxyiodide/bismuth oxybromide composite photocatalyst: respectively adding bismuth oxyiodide and bismuth oxybromide into ethanol, carrying out ultrasonic treatment for 1-2h, dropwise adding a bismuth oxyiodide solution into a bismuth oxybromide solution after the ultrasonic treatment is finished, continuously carrying out ultrasonic treatment on the mixed solution for 2-3 h, dropwise adding acetone into the mixed solution, carrying out magnetic stirring for 24h, precipitating, and drying at 60 ℃ for 12h to obtain the composite photocatalyst.
2. The method for preparing the bismuth oxyiodate/bismuth oxybromide composite photocatalyst according to claim 1, wherein the molar mass ratio of bismuth nitrate to potassium iodate in the step 1 is 1:1.
3. The method for preparing the bismuth oxyiodide/bismuth oxybromide composite photocatalyst according to claim 1 or 2, wherein the mass ratio of bismuth nitrate to cetyltrimethylammonium bromide in the step 2 is 1:1.
4. The preparation method of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst according to claim 1 or 2, wherein the mass ratio of the bismuth oxyiodide to the bismuth oxybromide in the step 3 is 1: 1-1.4.
5. The preparation method of the bismuth oxyiodide/bismuth oxybromide composite photocatalyst according to claim 1 or 2, which is characterized in that in the step 3, bismuth oxyiodide and bismuth oxybromide are respectively added into ethanol, and the solid-liquid volume ratio of bismuth oxyiodide or bismuth oxybromide to ethanol is 1: 150-200.
6. The method for preparing the bismuth oxyiodide/bismuth oxybromide composite photocatalyst according to claim 1 or 2, wherein the acetone is added dropwise in the step 3, and the volume fraction of the acetone in the final mixed solution is 40-60%.
7. The application of the bismuth oxyiodate/bismuth oxybromide composite photocatalyst prepared by the preparation method of any one of claims 1 to 6 is characterized in that the preparation method comprises the following steps:
(1) weighing a certain amount of bismuth oxyiodide/bismuth oxybromide photocatalyst, and adding the photocatalyst into a colorimetric tube;
(2) preparing a malachite green solution and adding the malachite green solution into a colorimetric tube;
(3) placing the colorimetric tube into a photocatalytic reactor, and stirring under a dark condition to ensure that the system achieves absorption/desorption balance; then turning on a light source, sampling the mixed solution at intervals under magnetic stirring, centrifuging, taking supernatant, and filtering by using a needle filter to obtain clarified liquid;
(4) the absorbance of the solution was measured using an ultraviolet-visible spectrophotometer, and the degradation rate was calculated.
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