CN114515582B - 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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CN114515582B
CN114515582B CN202210171015.9A CN202210171015A CN114515582B CN 114515582 B CN114515582 B CN 114515582B CN 202210171015 A CN202210171015 A CN 202210171015A CN 114515582 B CN114515582 B CN 114515582B
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bismuth
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CN114515582A (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, performing hydrothermal reaction, and performing post-treatment 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 preparation method, the bismuth quantum dot/bismuth oxyhalide composite material is prepared by regulating and controlling the adding molar ratio of bismuth salt to halogen salt and adding the bismuth salt precursor in large proportion and excessive amount, and the preparation method is low in energy consumption and simple in operation. The bismuth quantum dots in the obtained bismuth quantum dot/bismuth oxyhalide composite material are uniformly dispersed and smaller in size, the diameter range is 0.152-0.581 nm, the average diameter is 0.317nm, and the bismuth quantum dot/bismuth oxyhalide composite material has higher 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 rapid development of industrialization and city, environmental pollution is increasingly serious, and the problem becomes a hot spot to be solved in the global urgency. Therefore, there is an urgent need to develop an efficient "green" technique to contain the threat and harm of environmental pollution. The photocatalysis technology is one of the most effective green methods for solving the environmental pollution problem, and the core of the technology is the reasonable design and development of high-performance photocatalysts.
The bismuth-based material is a photocatalyst with visible light response which is 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 material (bisox, x=cl, br, I) is a novel layered bismuth-based material, and [ Bi2O2] layers and dihalogen layers in the crystal structure thereof are staggered, so that the bismuth oxyhalide material has a unique photoelectric effect, and has been widely paid attention to researchers. 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 limits the practical application of the intrinsic BiOX in the environmental photocatalysis technology. At present, researchers develop various strategies such as component adjustment, morphology control, heterojunction structure construction and the like to modify the BiOX, wherein noble metal loading (such as gold, silver, platinum and the like) is taken as an effective means, the photocatalytic performance of the BiOX can be remarkably improved, but the preparation cost of the photocatalyst is higher after noble metal materials are introduced.
Semi-metallic bismuth is similar to noble metal materials, has Surface Plasmon Resonance (SPR) characteristics, and has stable photocatalytic performance. Related researches indicate that the Bi/BiOX composite material promotes the flow of interfacial charges by constructing a Schottky barrier on the interface between the semi-metal Bi and the BiOX, and separates photoinduced carriers by taking the semi-metal Bi as an electron trap, thereby improving the photocatalytic performance of the catalyst. However, the construction of the semi-metal Bi and bismuth oxyhalide composite material is usually carried out by adopting a post-precipitation method so far, and the construction is complex, time-consuming and energy-consuming. Meanwhile, due to the incompleteness of the construction method, the Bi particles which are usually formed are large in diameter and easy to agglomerate (in the micrometer or hundreds of nanometer scale range), and the quantum scale effect is difficult to fully utilize to further improve the photocatalysis performance of the composite material. Therefore, how to quickly construct the high-dispersion bismuth quantum dot/bismuth oxyhalide composite material by a one-step method is a problem to be solved in the field.
Disclosure of Invention
The invention aims at solving 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 photocatalysis performance of the composite material is difficult to improve by fully utilizing quantum scale effect, and provides a preparation method of the 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 art and has low energy consumption, and the obtained composite material has excellent photocatalytic performance.
Another object of the invention is to provide a bismuth quantum dot/bismuth oxyhalide composite material.
Another object of the invention is to provide the use of the bismuth quantum dot/bismuth oxyhalide composite material described above as a photocatalyst.
The above object of the present invention is achieved by the following technical solutions:
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, performing hydrothermal reaction, and performing post-treatment 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 molar ratio of bismuth salt to halogen salt is regulated and controlled, and the bismuth salt precursor is excessively added in a large proportion, wherein a small amount of bismuth salt and halogen salt form an ultrathin two-dimensional bismuth oxyhalide structure based on 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 nano-sheet in situ, so that the in-situ nucleation of the zero-dimensional bismuth quantum dot is realized. Meanwhile, the surfactant added into the solution is also used as a dispersing agent, so that the high dispersion of the bismuth quantum dots on the bismuth oxyhalide nanosheets is ensured, and agglomeration is avoided.
Bismuth salt is adsorbed on the surface of bismuth oxyhalide nano-sheet in situ, so that in-situ nucleation of zero-dimensional bismuth quantum dots can be realized, but when the dosage of bismuth salt is too small, the formation quantity of bismuth quantum dots is too small; when the dosage of bismuth salt is too large, the bismuth quantum dots are easy to agglomerate, and partial large-size bismuth microspheres are generated, so that the quantum size effect is weakened.
Preferably, the molar ratio of bismuth salt to halogen salt is (150-250): 1.
more preferably, the molar ratio of bismuth salt to 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 hours.
Preferably, the molar ratio of bismuth salt to surfactant is (375-1900): 1.
more preferably, the molar ratio of bismuth salt to surfactant is 1500:1.
conventional bismuth salts, halogen salts and surfactants in the art can be used in the present invention, typically, the bismuth salts are 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 one or more selected from polyvinylpyrrolidone, cetyltrimethylammonium bromide and cetyltrimethylammonium chloride.
The solvent of the present invention may be any solvent conventional in the art, and typically, the solvent is one or more selected from glycerol, ethanol, mannitol, methanol, and water.
Preferably, the solvent is selected from a mixed solution of glycerol and water, wherein the volume ratio of the glycerol to the water in the mixed solution is 1:1.
the post-treatment of the invention 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 in 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:
according to the preparation method, the surfactant is used as a dispersing agent, and the bismuth salt precursor is subjected to large-proportion excessive addition by regulating and controlling the addition molar ratio of the bismuth salt and the halogen salt to prepare the bismuth quantum dot/bismuth oxyhalide composite material, so that the preparation method is low in energy consumption and simple in operation. The bismuth quantum dots in the obtained bismuth quantum dot/bismuth oxyhalide composite material are uniformly dispersed and smaller in size, the diameter range is 0.152-0.581 nm, the average diameter is 0.317nm, and the bismuth quantum dot/bismuth oxyhalide composite material has higher 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 the distribution and diameter of Bi quantum dots, and b is the crystal face corresponding to the lattice spacing between 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 photo-catalytic degradation chart of rhodamine B under visible light irradiation of the BiOBr and Bi/BiOBr composite material prepared by the method.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
Example 1
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, vigorously stirred on a magnetic stirrer for 30 minutes until dissolved, 5mL NaBr (1 mM) (bismuth nitrate and sodium bromide) was slowly added dropwiseThe molar ratio of (2) is 200:1), stirring is continued for 30 minutes, the stirred solution is transferred into a 100mL reaction kettle liner, the reaction kettle is covered, the reaction kettle is kept at 160 ℃ for 6 hours, and finally, the Bi QDs/BiOBr is obtained after centrifugation and sample washing are carried out for three times and the reaction kettle is kept at 60 ℃ for 12 hours.
Example 2
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 10mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 100:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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 (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 3.5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 300:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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 (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) was poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 130 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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 (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 180 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.1g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 375:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.5g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone 1900:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h 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:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until dissolution, slowly dropwise adding 5mL NaCl (1 mM) (the molar ratio of bismuth nitrate to sodium chloride is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging, washing samples for three times, and keeping the reaction kettle at 60 ℃ for 12 h to obtain Bi QDs/BiOCl.
Example 9
The embodiment provides a preparation method of a bismuth quantum dot/bismuth oxyhalide composite material, which comprises the following steps:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL of glycerol, vigorously stirred on a magnetic stirrer for 30 minutes until dissolved, 5mL of NaI (1 mM) (molar ratio of bismuth nitrate to sodium iodide 200:1) was slowly added dropwise, stirring was continued for 30 minutes, and the stirred solution was moved to 100mAnd (3) after covering the reaction kettle in the liner of the reaction kettle of L, 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 the 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:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL mannitol, stirring vigorously on a magnetic stirrer for 30min until dissolution, slowly dropwise adding 5mL NaBr (1 mM) (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6h, and finally, centrifuging, washing samples for three times, and keeping the reaction kettle at 60 ℃ for 12 h 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 (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 In a beaker of O and 25mL glycerol, stirring vigorously on a magnetic stirrer for 30min until the NaBr (1 mM) is dissolved, slowly dropwise adding 5mL of NaBr (the molar ratio of bismuth nitrate to sodium bromide is 200:1), stirring continuously for 30min, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 16h, and finally, centrifuging and washing the sample three times, and keeping the reaction kettle at 60 ℃ for 12 h to obtain Bi QDs/BiOBr.
Comparative example 1
This comparative example 1 provides a preparation method of BiOBr, comprising the steps of:
0.486g (1 mmol) of Bi (NO) was measured out 3 ) 3 ·5H 2 O and 0.4g PVP (molar ratio of bismuth nitrate to polyvinylpyrrolidone: 1500:1) were poured into a container filled with 25mL H 2 O and 25mL of PrazimuthallyIn a beaker of alcohol, stirring vigorously on a magnetic stirrer for 30 minutes until the NaBr (1M) is dissolved, slowly dropwise adding 5mL of NaBr (1M) (the molar ratio of bismuth nitrate to sodium bromide is 1:5), stirring continuously for 30 minutes, transferring the stirred solution into a 100mL reaction kettle liner, covering the reaction kettle, keeping the reaction kettle at 160 ℃ for 6 hours, and finally, centrifuging, washing the sample for three times, and keeping the reaction kettle at 60 ℃ for 12 hours to obtain BiOBr.
In the comparative example, the BiOBr is prepared by excessive NaBr and cannot form a Bi QDs/BiOBr composite material.
Characterization and performance testing
The bismuth quantum dot/bismuth oxyhalide composite materials obtained in examples 1 to 11 and the material described in comparative example 1 were characterized and tested for performance as follows:
the bismuth quantum dot/bismuth oxyhalide composites obtained in examples 1 to 11 were subjected to crystal structure observation using an X-ray diffractometer (Rigaku SmartLab 9kW XRD with Cu ka 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 samples, all the BiOBr peaks were clearly shown and a new characteristic peak was observed at 2θ=27.26°, which was well-matched with the semi-metallic Bi (012) crystal plane (PDF, # 85-1331), indicating that the product produced was Bi/BiOBr. XRD of the bismuth quantum dot/bismuth oxyhalide composites described in examples 2-11 were substantially identical to example 1.
A high power transmission electron microscope image of the bismuth quantum dot/bismuth oxyhalide composite material described in example 1 is shown in fig. 2. Wherein, FIG. 2a is a graph of Bi quantum dot distribution and diameter, and FIG. 2b is a crystal plane corresponding to the lattice spacing of Bi and BiOBr, showing the successful preparation of Bi/BiOBr and the uniform dispersion of semi-metallic Bi on BiOBr nanoplatelets. TEM's of the bismuth quantum dot/bismuth oxyhalide composites described in examples 2-11 are substantially identical to example 1.
The elemental 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 presence of the elements Bi, O, br in Bi/BiOBr indicates that the elements Bi, O, br are uniformly dispersed in Bi/BiOBr. The elemental distribution maps of the bismuth quantum dot/bismuth oxyhalide composites described in examples 2-11 were substantially identical to example 1.
The photocatalytic activity of the bismuth quantum dot/bismuth oxyhalide composite material prepared in the example 1 and the bismuth oxybromide degradation rhodamine B (RhB) in the visible light as described in the comparative example 1 are adopted to test the photocatalytic activity, and the photocatalytic activity measuring method comprises the following steps: 10mg of the sample was dispersed in 100mL of RhB solution (10 mg/L) at 25℃and stirred in the dark for 30min before illumination, and after the mixture reached adsorption equilibrium, a xenon lamp with a 420nm cut-off filter was turned on to conduct a 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 irradiation of visible light are shown in fig. 4. As can be seen from FIG. 4, the degradation rate of Bi/BiOBr to RhB within 20min of illumination was 78.7%, and the degradation rate of BiOBr to RhB was 29.4%. The Bi/BiOBr composite material has better photocatalytic degradation effect on RhB. The degradation rate of the bismuth quantum dot/bismuth oxyhalide composite material in examples 2-11 to RhB is more than 50% in 20 min.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (8)

1. The preparation method of the bismuth quantum dot/bismuth oxyhalide composite material is characterized by comprising the following steps of:
mixing bismuth salt, halogen salt, a surfactant and a solvent, uniformly stirring, and performing solvothermal reaction to obtain a solution, and performing aftertreatment to obtain a bismuth quantum dot/bismuth oxyhalide composite material;
the molar ratio of the bismuth salt to the halogen salt is (150-250): 1;
the diameter of the bismuth quantum dots in the bismuth quantum dot/bismuth oxyhalide composite material is 0.152-0.581 nm;
the molar ratio of the bismuth salt to the surfactant is (375-1900): 1.
2. the method for preparing the bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the solvothermal reaction temperature is 130-180 ℃ and the reaction time is 4-16 h.
3. The method for preparing bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the bismuth salt is bismuth nitrate and/or bismuth trichloride.
4. The method for preparing 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.
5. The method for preparing bismuth quantum dot/bismuth oxyhalide composite material according to claim 1, wherein the surfactant is one or more selected from polyvinylpyrrolidone, cetyltrimethylammonium bromide and cetyltrimethylammonium chloride.
6. The method for preparing 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.
7. The bismuth quantum dot/bismuth oxyhalide composite material is characterized by being prepared by the method of any one of claims 1-6.
8. The use of the bismuth quantum dot/bismuth oxyhalide composite material as claimed in claim 7 as a photocatalyst for degrading organic pollutants.
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