CN114515582A - Bismuth quantum dot/bismuth oxyhalide composite material and preparation method and application thereof - Google Patents

Bismuth quantum dot/bismuth oxyhalide composite material and preparation method and application thereof Download PDF

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CN114515582A
CN114515582A CN202210171015.9A CN202210171015A CN114515582A CN 114515582 A CN114515582 A CN 114515582A CN 202210171015 A CN202210171015 A CN 202210171015A CN 114515582 A CN114515582 A CN 114515582A
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bismuth
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CN114515582B (en
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王俏
曹怡婷
余粤秘
张超
黄家豪
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Guangdong University of Technology
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Abstract

The invention discloses a bismuth quantum dot bismuth oxyhalide/composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing bismuth salt, halogen salt, a surfactant and a solvent, uniformly stirring, carrying out hydrothermal reaction, and carrying out aftertreatment on the obtained solution to obtain a bismuth quantum dot/bismuth oxyhalide composite material; the molar ratio of the bismuth salt to the halogen salt is (100-300): 1. according to the invention, the bismuth quantum dot/bismuth oxyhalide composite material is prepared by controlling the adding molar ratio of bismuth salt to halogen salt and adding the bismuth salt precursor in a large-proportion excessive manner, and the preparation method is low in energy consumption and simple to operate. The bismuth quantum dots in the bismuth quantum dot/bismuth oxyhalide composite material are uniformly dispersed and have small sizes, the diameter range of the bismuth quantum dots is 0.152-0.581 nm, the average diameter of the bismuth quantum dots is 0.317nm, and the bismuth quantum dots have high photocatalytic activity when being used for photocatalytic degradation of organic pollutants.

Description

Bismuth quantum dot/bismuth oxyhalide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a bismuth quantum dot/bismuth oxyhalide composite material and a preparation method and application thereof.
Background
In recent years, with the rapid development of industrialization and urbanization, the problem of environmental pollution is becoming more serious, and the problem becomes a hot point to be solved urgently in the world. Therefore, there is an urgent need to develop an efficient "green" technology to counter the threat and harm caused by environmental pollution. The photocatalytic technology is characterized in that solar energy is utilized to drive a series of oxidation-reduction reactions, so that various organic pollutants in the environment are effectively degraded, and the problem of secondary pollution is not generated.
The bismuth-based material is a photocatalyst with visible light response widely researched at present, and has the advantages of high photocatalytic efficiency, high chemical stability, low cost, no toxicity and the like. Among them, bismuth oxyhalide materials (BiOX, X ═ Cl, Br, and I) have been widely noticed by researchers as a novel layered bismuth-based material, because [ Bi2O2] layers and double halogen layers in the crystal structure thereof are staggered, thereby having a unique photoelectric effect. However, the intrinsic BiOX still has the defects of weak light absorption capability, high recombination rate of photo-generated electron-hole pairs and the like, and the practical application of the intrinsic BiOX in the environmental photocatalysis technology is limited. At present, researchers develop various strategies such as component regulation, morphology control and heterojunction structure construction to modify the BiOX, wherein noble metal load (such as gold, silver, platinum and the like) is used as an effective means to remarkably improve the photocatalytic performance of the BiOX, but the preparation cost of the photocatalyst is high after the noble metal material is introduced.
The semimetal bismuth has Surface Plasmon Resonance (SPR) characteristics similar to those of noble metal materials, and has stable photocatalytic performance. Relevant researches indicate that the Bi/BiOX composite material promotes interface charge flow by constructing a Schottky barrier on the interface of the semimetal Bi and the BiOX, and takes the semimetal Bi as an electron trap to separate photoinduced carriers, so that the photocatalytic performance of the catalyst is improved. However, the construction of the composite material of semimetal Bi and bismuth oxyhalide so far is usually carried out by post-precipitation, which is complicated, time-consuming and energy-consuming. Meanwhile, due to the incomplete construction method, the commonly formed Bi particles have large diameters and are easy to agglomerate (within the range of micron or hundreds of nanometer scale), and the quantum scale effect is difficult to be fully utilized to further improve the photocatalytic performance of the composite material. Therefore, how to rapidly construct a high-dispersion bismuth quantum dot/bismuth oxyhalide composite material by a one-step method is an urgent problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the problems that the existing Bi/BiOX composite material is complex in preparation process, the prepared Bi/BiOX composite material is large in Bi particle diameter, and the photocatalytic performance of the composite material is difficult to improve by fully utilizing the quantum scale effect, and provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material. The method can quickly construct the high-dispersion bismuth quantum dot/bismuth oxyhalide composite material, simplifies the prior process, has low energy consumption, and ensures that the obtained composite material has excellent photocatalytic performance.
Another object of the present invention is to provide a bismuth quantum dot/bismuth oxyhalide composite material.
The invention also aims to provide the application of the bismuth quantum dot/bismuth oxyhalide composite material as a photocatalyst.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material comprises the following steps:
mixing bismuth salt, halogen salt, a surfactant and a solvent, uniformly stirring, carrying out hydrothermal reaction, and carrying out aftertreatment on the obtained solution to obtain a bismuth quantum dot/bismuth oxyhalide composite material;
the molar ratio of the bismuth salt to the halogen salt is (100-300): 1.
the bismuth salt precursor is added in a large-proportion excessive manner by regulating the adding molar ratio of bismuth salt to halogen salt, wherein a small amount of bismuth salt and halogen salt form an ultrathin two-dimensional bismuth oxyhalide structure based on the regulation and control of a surfactant in the hydrothermal reaction process; meanwhile, a large proportion of the residual bismuth salt is adsorbed on the surface of the bismuth oxyhalide nanosheet in situ, so that in-situ nucleation of the zero-dimensional bismuth quantum dots is realized. Meanwhile, the surfactant added into the solution also serves as a dispersing agent, so that the high dispersion of the bismuth quantum dots on the bismuth oxyhalide nanosheets is ensured, and the agglomeration is avoided.
Bismuth salt is adsorbed on the surface of the bismuth oxyhalide nanosheet in situ, so that in-situ nucleation of the zero-dimensional bismuth quantum dots can be realized, but when the using amount of the bismuth salt is too small, the forming amount of the bismuth quantum dots is too small; when the dosage of the bismuth salt is excessive, the bismuth quantum dots are easy to agglomerate, and a part of large-size bismuth microspheres are generated, so that the quantum size effect is weakened.
Preferably, the molar ratio of the bismuth salt to the halogen salt is (150-250): 1.
more preferably, the molar ratio of the bismuth salt to the halogen salt is 200: 1.
preferably, the hydrothermal reaction temperature is 130-180 ℃, and the reaction time is 4-16 h.
More preferably, the hydrothermal reaction temperature is 160 ℃ and the reaction time is 6 h.
Preferably, the molar ratio of the bismuth salt to the surfactant is (375-1900): 1.
more preferably, the molar ratio of the bismuth salt to the surfactant is 1500: 1.
bismuth salts, halogen salts and surfactants conventional in the art may be used in the present invention, typically the bismuth salt is bismuth nitrate and/or bismuth trichloride; the halogen salt is selected from one or more of potassium chloride, potassium iodide, sodium bromide and sodium chloride; the surfactant is selected from one or more of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride.
The solvent used in the present invention is selected from conventional solvents in the art, and generally, the solvent is selected from one or more of glycerol, ethanol, mannitol, methanol and water.
Preferably, the solvent is selected from a mixed solution of glycerol and water, and the volume ratio of the glycerol to the water in the mixed solution is 1: 1.
the post-treatment of the invention specifically comprises centrifugation, washing and drying.
The invention also provides the bismuth quantum dot/bismuth oxyhalide composite material prepared by the method.
The bismuth quantum dot/bismuth oxyhalide composite material has higher photocatalytic activity when being used as a photocatalyst for photocatalytic degradation of organic pollutants, so that the application of the bismuth quantum dot/bismuth oxyhalide composite material as the photocatalyst for degradation of organic pollutants is also within the protection scope of the invention.
Preferably, the organic pollutant is one or more of rhodamine B, methylene blue, methyl orange, malachite green, bisphenol A, parachlorophenol and sulfamethoxazole.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the surfactant as the dispersant, and the bismuth salt precursor is excessively added in a large proportion by regulating the adding molar ratio of the bismuth salt to the halogen salt to prepare the bismuth quantum dot/bismuth oxyhalide composite material. The bismuth quantum dots in the bismuth quantum dot/bismuth oxyhalide composite material are uniformly dispersed and have small sizes, the diameter range of the bismuth quantum dots is 0.152-0.581 nm, the average diameter of the bismuth quantum dots is 0.317nm, and the bismuth quantum dots have high photocatalytic activity when being used for photocatalytic degradation of organic pollutants.
Drawings
Fig. 1 is an X-ray diffraction pattern of the bismuth quantum dot/bismuth oxyhalide composite material prepared in example 1 of the present invention.
FIG. 2 is a high-power transmission electron microscope image of the bismuth quantum dot/bismuth oxyhalide composite material prepared in example 1 of the present invention. Wherein a is a Bi quantum dot distribution and diameter size diagram, and b is a crystal face corresponding to the lattice spacing of Bi and BiOBr.
Fig. 3 is an element distribution map of the bismuth quantum dot/bismuth oxyhalide composite material prepared in example 1 of the present invention.
FIG. 4 is a diagram showing the photocatalytic degradation of the BiOBr and Bi/BiOBr composite material prepared by the invention to rhodamine B under the irradiation of visible light.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H 2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 160 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 2
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 10mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 100:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 160 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 3
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1mmol) of Bi (NO) was measured3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) was poured into the flask25mL H2In a beaker containing O and 25mL of glycerol, stirring vigorously for 30 minutes on a magnetic stirrer until the solution is dissolved, slowly and dropwise adding 3.5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 300:1), stirring continuously for 30 minutes, transferring the stirred solution into a 100mL reaction kettle lining, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6 hours, and finally, centrifuging and washing samples three times, and keeping the reaction kettle at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 4
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1mmol) of Bi (NO) was measured3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 130 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 5
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1mmol) of Bi (NO) was measured3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) was poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 180 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 6
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.1g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 375: 1) were poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 160 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 7
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.5g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1900: 1) were poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, the mixture is vigorously stirred for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1) is slowly dropped, the mixture is continuously stirred for 30 minutes, the stirred solution is transferred to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 160 ℃ for 6 hours, and finally, the sample is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 8
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2O and 25mL of glycerin, stirring vigorously for 30 minutes on a magnetic stirrer until the solution is dissolved, slowly adding dropwise 5mL of NaCl (1mM) (molar ratio of bismuth nitrate to sodium chloride is 200:1), stirring continuously for 30 minutes, transferring the stirred solution into a 100mL reaction vessel lining, covering the reaction vessel, and keeping at 160 ℃ for 6 hours, preferably 160 ℃ for 6 hours After that, after centrifugation, sample washing three times, and holding at 60 ℃ for 12 hours, Bi QDs/BiOCl was obtained.
Example 9
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1mmol) of Bi (NO) was measured3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2In a beaker containing O and 25mL of glycerol, stirring vigorously for 30 minutes on a magnetic stirrer until the solution is dissolved, slowly dropwise adding 5mL of NaI (1mM) (the molar ratio of bismuth nitrate to sodium iodide is 200:1), stirring continuously for 30 minutes, transferring the stirred solution into a 100mL reaction kettle lining, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6 hours, and finally, centrifuging and washing the sample for three times, and keeping the reaction kettle at 60 ℃ for 12 hours to obtain Bi QDs/BiOI.
Example 10
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2O and 25mL mannitol, stirring vigorously for 30 minutes on a magnetic stirrer until the solution is dissolved, slowly and dropwise adding 5mL NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30 minutes, transferring the stirred solution into a 100mL reaction kettle lining, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6 hours, and finally, centrifuging and washing samples for three times, and keeping the reaction kettle at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Example 11
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1mmol) of Bi (NO) was measured3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) was poured into a flask containing 25mL of H2In a beaker of O and 25mL of glycerol, vigorously stirred on a magnetic stirrerStirring for 30 minutes until the solution is dissolved, slowly and dropwise adding 5mL of NaBr (1mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1), continuing stirring for 30 minutes, transferring the stirred solution into a 100mL reaction kettle lining, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 16 hours, and finally, centrifuging and washing samples for three times, and keeping the reaction kettle at 60 ℃ for 12 hours to obtain Bi QDs/BiOBr.
Comparative example 1
The comparative example 1 provides a method for preparing BiOBr, comprising the steps of:
a weighed amount of 0.486g (1mmol) of Bi (NO)3)3·5H2O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1500: 1) were poured into a flask containing 25mL of H2And O and 25mL of glycerol are stirred vigorously for 30 minutes on a magnetic stirrer until the mixture is dissolved, 5mL of NaBr (1M) is slowly dropped (the molar ratio of bismuth nitrate to sodium bromide is 1:5), the mixture is stirred continuously for 30 minutes, the stirred solution is moved to a 100mL reaction kettle lining, the reaction kettle is covered and kept at 160 ℃ for 6 hours, and finally, the mixture is centrifuged and washed three times and kept at 60 ℃ for 12 hours to obtain BiOBr.
In the comparative example, excessive NaBr can not form Bi QDs/BiOBr composite material, and BiOBr is prepared.
Characterization and Performance testing
The bismuth quantum dot/bismuth oxyhalide composite materials obtained in the embodiments 1-11 and the material described in the comparative example 1 are subjected to characterization and performance tests, and the specific characterization and performance tests are as follows:
the crystal structure of the bismuth quantum dot/bismuth oxyhalide composite materials obtained in examples 1 to 11 was observed by an X-ray diffractometer (Rigaku SmartLab 9kW XRD with Cu K α radiation (λ ═ 0.15418 nm)).
The X-ray diffraction patterns of the bismuth quantum dot/bismuth oxyhalide composite material described in example 1 and the bismuth oxybromide described in comparative example 1 are shown in fig. 1. As can be seen from fig. 1, in the BiOBr standard card, typical peaks occur at 10.91 °, 31.72 °, 32.24 °, 46.90 ° and 57.16 °, pointing to the (001), (012), (110), (113) and (212) crystal planes (PDF #78-0348), respectively. For the Bi/BiOBr sample, all BiOBr peaks are clearly shown, and a new characteristic peak is observed at 27.26 ° 2 θ, which is in good agreement with the semi-metallic Bi (012) crystal plane (PDF, #85-1331), indicating that the product produced is Bi/BiOBr. XRD of the bismuth quantum dot/bismuth oxyhalide composite materials in examples 2-11 is substantially the same as that of example 1.
A high power transmission electron micrograph of the bismuth quantum dot/bismuth oxyhalide composite material of example 1 is shown in fig. 2. Wherein, fig. 2a is a diagram of the distribution and diameter of Bi quantum dots, and fig. 2b is a crystal face corresponding to the lattice spacing of Bi and BiOBr, which shows the successful preparation of Bi/BiOBr and the uniform dispersion of semimetal Bi on the BiOBr nano-chip. The TEM of the bismuth quantum dot/bismuth oxyhalide composite material of the embodiments 2-11 is basically the same as that of the embodiment 1.
The element distribution map of the bismuth quantum dot/bismuth oxyhalide composite material described in example 1 is shown in fig. 3. As can be seen from FIG. 3, the elements Bi, O and Br are present in Bi/BiOBr, indicating that the elements Bi, O and Br are uniformly dispersed in Bi/BiOBr. The element distribution map of the bismuth quantum dot/bismuth oxyhalide composite material in the examples 2 to 11 is substantially the same as that in the example 1.
The bismuth quantum dot/bismuth oxyhalide composite material prepared in example 1 and bismuth oxybromide described in comparative example 1 are used for degrading rhodamine B (RhB) under visible light to test the photocatalytic activity, and the photocatalytic activity is determined by the following method: 10mg of the sample was dispersed in 100mL of RhB solution (10mg/L) at 25 ℃, and stirred in the dark for 30min before illumination to allow the mixture to reach adsorption equilibrium, and then a xenon lamp with a 420nm cut-off filter was turned on to perform the photocatalytic degradation experiment.
The photocatalytic degradation patterns of the bismuth quantum dot/bismuth oxyhalide composite material described in example 1 and the bismuth oxybromide described in comparative example 1 on rhodamine B (RhB) under visible light irradiation are shown in FIG. 4. As can be seen from FIG. 4, the degradation rate of RhB by Bi/BiOBr is 78.7% and the degradation rate of RhB by BiOBr is 29.4% within 20min of illumination. The Bi/BiOBr composite material is shown to have better effect of photocatalytic degradation of RhB. The degradation rate of the bismuth quantum dot/bismuth oxyhalide composite material to RhB within 20min is more than 50%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a bismuth quantum dot/bismuth oxyhalide composite material is characterized by comprising the following steps:
mixing bismuth salt, halogen salt, a surfactant and a solvent, uniformly stirring, carrying out hydrothermal reaction, and carrying out aftertreatment on the obtained solution to obtain a bismuth quantum dot/bismuth oxyhalide composite material;
The molar ratio of the bismuth salt to the halogen salt is (100-300): 1.
2. The preparation method of the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the molar ratio of the bismuth salt to the halogen salt is (150-250): 1.
3. The preparation method of the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the hydrothermal reaction temperature is 130-180 ℃ and the reaction time is 4-16 h.
4. The preparation method of the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the molar ratio of the bismuth salt to the surfactant is (375-1900): 1.
5. the method of claim 1, wherein the bismuth salt is bismuth nitrate and/or bismuth trichloride.
6. The method for preparing the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the halogen salt is one or more selected from potassium chloride, potassium iodide, sodium bromide and sodium chloride.
7. The method of claim 1, wherein the surfactant is selected from one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, and cetyltrimethylammonium chloride.
8. The method for preparing the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the solvent is one or more selected from glycerol, ethanol, mannitol, methanol and water.
9. A bismuth quantum dot/bismuth oxyhalide composite material, which is characterized by being prepared by the method of any one of claims 1 to 8.
10. Use of the bismuth quantum dot/bismuth oxyhalide composite material of claim 9 as a photocatalyst to degrade organic contaminants.
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