CN113546688B - Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6Visible light catalyst and preparation method thereof - Google Patents

Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6Visible light catalyst and preparation method thereof Download PDF

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CN113546688B
CN113546688B CN202110835966.7A CN202110835966A CN113546688B CN 113546688 B CN113546688 B CN 113546688B CN 202110835966 A CN202110835966 A CN 202110835966A CN 113546688 B CN113546688 B CN 113546688B
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顾文秀
李倩
李海新
宋启军
赵媛
王婵
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Jiangnan University
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Abstract

The invention discloses Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6A visible light catalyst and a preparation method thereof belong to the technical field of environment and energy. The invention prepares Bi-MOF-M microspheres through self-assembly, and grows a layer of petal-shaped Bi on the surface layer of the Bi-MOF-M microspheres through interface in-situ growth2MoO6Forming a chemical bonding type heterojunction to prepare the micro-nano graded flower-shaped spherical Bi-MOF-M/Bi2MoO6A visible light photocatalyst. The composite visible-light-induced photocatalyst is simple and convenient to prepare, environment-friendly, high in stability, free of residues in wastewater, high in visible-light catalytic activity, capable of efficiently degrading various organic dye wastewater and high-concentration antibiotic wastewater under the irradiation of visible light, simple in wastewater treatment process, capable of being recycled, greatly reduced in cost and good in industrial application prospect.

Description

Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6Visible light catalyst and preparation method thereof
Technical Field
The invention relates to Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6A visible light catalyst and a preparation method thereof belong to the technical field of environment and energy.
Background
With the rapid development of modern industry, the quantity and types of organic pollutants difficult to biodegrade are increasing day by day, which has great influence on natural ecological environment, life and health of people, especially pollutants generated in chemical industry, printing and dyeing, medicine and other industries are increasing along with the development of society. Due to the influence of technical and economic factors, the current wastewater treatment mainly adopts chemical methods, physical methods and other methods, but the current high efficiency and high requirements on pollutant treatment cannot be met. Organic wastewater which is generated in the industries of chemical industry, printing and dyeing, medicine and the like and is difficult to treat needs new green and efficient treatment technology.
Photocatalysis is a green energy technology, and has attracted wide attention of domestic and foreign scholars due to strong processing capacity, mild reaction conditions and no secondary pollution. A photocatalyst is essentially a semiconductor material that, when absorbing light with energy greater than or equal to its bandgap energy, excites electrons on the valence band to jump to the conduction band, forming photogenerated hole-electron pairs. These holes and electrons, i.e., carriers having strong oxidation or reduction ability, can decompose chemical substances adsorbed on the surface of the semiconductor and are finally mineralized into H2O and CO2And the like. At present, the research in the field of photocatalysis is more intensive, and nano titanium dioxide-based photocatalysts have the characteristics of stable chemical property, abrasion resistance, light corrosion resistance, low cost, no toxicity and the like, and are widely applied to the preparation of photolysis water and solar cells and the like besides being used for degrading organic matters and sterilizing. However, titanium dioxide has too wide a band gap energy (3.2eV), and has an excitation wavelength of 387.5nm, which is in the ultraviolet region. For the solar spectrum, the main energy is concentrated in the wavelength range of 460nm to 600nm, and the proportion of ultraviolet light is less than 5 percent, so that the utilization efficiency of the titanium dioxide to sunlight is extremely low; the recombination probability of the photo-generated carriers of the titanium dioxide is high, so that the catalytic efficiency is reduced; in addition, when the wastewater is treated, titanium dioxide nanoparticles suspended in the system are easy to agglomerate and inactivate, and are difficult to recover after the reaction is finished, so that the titanium dioxide nanoparticles are difficult to recycle. Therefore, from the perspective of fully utilizing sunlight, the preparation of the visible-light-driven photocatalyst which is easy to recycle and has high photoelectric conversion efficiency has important significance in the fields of energy and environment.
In recent years, bismuth-based semiconductor materials have attracted great attention in the field of photocatalysis due to their unique electronic structure and appropriate photoresponsive band gap, such as BiOX (X ═ Cl, Br, I), Bi2MoO6，Bi2WO6，BiVO4And the like. Bulk bismuth-based semiconductors have poor catalytic performance and are therefore being investigatedThe nanometer bismuth-based semiconductor photocatalyst is prepared by controlling the shape, and the catalytic activity is better improved, such as a nanometer sheet, a nanometer rod, a nanometer flower and the like. However, the nano-scale catalyst has the disadvantages of easy agglomeration and difficult recovery in practical application, and has great limitation in the practical application of photocatalysis.
Metal Organic Frameworks (MOFs), which are two-dimensional or three-dimensional porous crystalline materials formed by coordination of metal ions and organic ligands, have been widely used in the fields of catalysis, sensing, adsorption, proton conduction, etc. due to their advantages of high specific surface area, high porosity, adjustable structure, etc., with the continuous development of MOFs, the application fields of MOFs materials are also continuously widened, and good application prospects are shown in the field of photocatalysis. Bismuth not only has the advantages of no toxicity, no harm, abundant reserves, low price and the like, but also has flexible and various coordination configurations, and is beneficial to constructing various MOFs materials. Hitherto, as the bismuth-based MOFs, CAU-7, CAU-17, CAU-31, 32, 33, 35, NOTT-220, Bi-NU-901 and the like have been reported. By summarizing the research work, the relevant research of bismuth-based MOFs is mostly focused on material preparation and structure analysis, the property research of the material is less, only the gas adsorption and some basic optical properties are involved, the research on the photocatalytic performance is less, the bismuth-based MOFs composite photocatalyst has multiple advantages of excellent photocatalytic performance of bismuth-based materials, structural advantages of MOFs materials and the like, the existing problems in photocatalysis are expected to be solved, and the novel high-performance visible light catalyst is obtained.
Disclosure of Invention
In order to solve the two technical problems that the photo-generated carriers of the existing photocatalyst are easy to compound and the nano photocatalyst is difficult to recover and recycle, the invention prepares a nano rod self-assembled micro-nano hierarchical structure Bi-MOF microsphere (Bi-MOF-M) by an ethylene glycol assisted solvothermal method, and then grows a layer of petal-shaped Bi on the surface layer of the Bi-MOF-M by a homologous growth method2MoO6To prepare the chemical bonding type heterojunction composite photocatalyst Bi-MOF-M/Bi2MoO6Prepared Bi-MOF-M/Bi2MoO6The composite photocatalyst has a micro-nano graded flower ball structure, and can protectThe advantages of high activity of the nano-scale particles are maintained, and the defects that nano-scale materials are easy to agglomerate and difficult to recycle are overcome; the formed chemical bonding type heterojunction can effectively widen the spectral absorption range of the obtained composite photocatalyst and improve the absorption strength of the composite photocatalyst, and can effectively promote the separation of photo-generated electrons and holes by forming a favorable interface electric field, so that the visible light catalytic performance of the obtained composite photocatalyst is greatly improved. Prepared Bi-MOF-M/Bi2MoO6The visible light catalyst has the advantages of simple preparation process, low cost, environmental friendliness and good industrial application prospect.
The technical scheme of the invention is as follows: Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6A method of preparing a visible-light-driven photocatalyst, the method comprising: preparing Bi-MOF-M microspheres self-assembled by Bi-MOF nanorods through glycol-assisted solvothermal reaction, taking the Bi-MOF-M microspheres as a homologous template, and growing a layer of petal-shaped Bi on the surface layer of the microspheres in situ2MoO6The micro-nano graded flower spherical chemical bonding type heterojunction visible light catalyst Bi-MOF-M/Bi is simply and conveniently prepared2MoO6。
In particular to Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6The preparation method of the visible light photocatalyst comprises the following steps:
(1) preparation of Bi-MOF microspheres (Bi-MOF-M): respectively dissolving a bismuth source and terephthalic acid in ethylene glycol and N, N-dimethylformamide to obtain solution A and solution B, dropwise adding the solution B into the solution A, stirring for 1-3 h, transferring to a hydrothermal reaction kettle, reacting at 120-160 ℃ for 12-18 h, cooling after the reaction is finished, carrying out solid-liquid separation, washing with water and ethanol for several times respectively, and drying to obtain the Bi-MOF microspheres (Bi-MOF-M);
(2)Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: dispersing the Bi-MOF-M prepared in the step (1) in ethanol to obtain a solution C, dissolving molybdate in ethylene glycol to obtain a solution D, dropwise adding the solution D into the solution C, stirring for 1-3 h, transferring to a hydrothermal reaction kettle, reacting at 120-180 ℃ for 12-18 h, cooling after the reaction is finished, carrying out solid-liquid separation, and respectively using waterWashing with ethanol for several times, and drying to obtain the Bi-MOF-M/Bi2MoO6A visible light photocatalyst.
In one embodiment of the present invention, the concentration of the bismuth source in the solution A is 0.025 to 0.125 mmol/mL.
In one embodiment of the present invention, the concentration of terephthalic acid in the solution B is 0.03 to 0.17 mmol/mL.
In one embodiment of the invention, the molar ratio of the bismuth source to the terephthalic acid is 1-5: 1-5.
In one embodiment of the invention, the bismuth source is preferably Bi (NO)3)3·5H2O。
In one embodiment of the present invention, the stirring is preferably performed at 10 to 40 ℃.
In one embodiment of the invention, the solid-liquid separation is preferably filtration.
In one embodiment of the present invention, the washing with water and ethanol, respectively, is preferably: washing with deionized water for 1-2 times, and washing with ethanol for 1-2 times.
In one embodiment of the invention, the drying is preferably vacuum drying, and the drying temperature is 50-80 ℃.
In one embodiment of the invention, the content of Bi-MOF-M in the liquid C is 2.5-7.5 mg/mL.
In one embodiment of the present invention, the concentration of molybdate in the solution D is 0.005 to 0.025 mmol/mL.
In one embodiment of the invention, the mass molar ratio of the Bi-MOF-M to the molybdate is 1-3: 1-5 g/mmol.
In one embodiment of the invention, the molybdate is preferably Na2MoO4·2H2O。
The invention also provides Bi-MOF-M/Bi prepared by the preparation method2MoO6A visible light photocatalyst.
The invention also provides the Bi-MOF-M/Bi2MoO6The application of visible light catalyst in treating organic waste water.
The invention also provides a method for treating organic wastewater, which uses the Bi-MOF-M/Bi2MoO6The visible light photocatalyst acts as a photocatalyst.
In one embodiment of the present invention, the method for treating organic wastewater comprises the steps of: mixing Bi-MOF-M/Bi2MoO6The visible light catalyst is added into an organic wastewater sample, and the dosage is as follows: 0.5-1.0 g/L, and degrading under the irradiation of visible light.
In one embodiment of the present invention, the organic wastewater comprises organic dye wastewater and antibiotic wastewater.
The invention has the beneficial effects that:
compared with the prior art, the preparation method has the advantages that the Bi-MOF-M microspheres are prepared through self-assembly, and a layer of petal-shaped Bi grows on the surface layer of the Bi-MOF-M through in-situ growth of the interface2MoO6Forming a chemically bonded heterojunction to obtain Bi-MOF-M/Bi2MoO6Visible light catalyst, Bi-MOF-M/Bi2MoO6The visible light catalyst has a micro-nano graded flower-sphere structure, can keep the advantage of high activity of nano-scale particles, and can overcome the defects that nano-scale materials are easy to agglomerate and difficult to recycle; the formed chemical bonding type heterojunction not only can effectively widen the spectrum absorption range and improve the absorption strength, but also can effectively promote the separation of photo-generated electrons and holes by forming a favorable interface electric field, thereby greatly improving the visible light catalytic performance of the obtained composite photocatalyst.
The composite visible-light-driven photocatalyst prepared by the invention has stable performance and no residue in wastewater; the visible light has high catalytic activity, can efficiently degrade various organic dye wastewater and high-concentration antibiotic wastewater under the irradiation of visible light, has simple wastewater treatment process, can greatly reduce the cost, is simple and convenient to prepare, is environment-friendly, is easy to recycle, and has good industrial application prospect. This Bi-MOF-M/Bi2MoO6The preparation method of the visible-light-driven photocatalyst, the product and the application belong to pioneering work.
Drawings
FIG. 1 is an SEM picture of Bi-MOF-M obtained in example 3 of the present invention.
FIG. 2 shows Bi-MOF-M/Bi obtained in example 3 of the present invention2MoO6SEM image of (d).
FIG. 3 shows Bi-MOF-M and Bi-MOF-M/Bi obtained in example 3 of the present invention2MoO6The ultraviolet-visible diffuse reflection spectrum of the visible light catalyst is shown in the specification, wherein 1 is Bi-MOF-M, and 2 is Bi-MOF-M/Bi2MoO6。
FIG. 4 shows Bi-MOF-M/Bi obtained in example 3 of the present invention2MoO6A relation graph of the removal efficiency and the recycling times of the visible light catalyst on the methylene blue wastewater and the tetracycline hydrochloride wastewater, wherein 1 is the methylene blue, and 2 is the tetracycline hydrochloride.
FIG. 5 is an SEM picture of the rod-shaped Bi-MOF obtained in comparative example 3.
FIG. 6 is an SEM photograph of the dumbbell-shaped bouquet Bi-MOF obtained in comparative example 4.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
This example is Bi-MOF-M/Bi2MoO6Preparation and application of visible light catalyst. The specific process is as follows:
preparation of Bi-MOF microspheres (Bi-MOF-M): 1mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 1mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the obtained B into A, stirring at room temperature for 1h, then transferring to a hydrothermal reaction kettle, reacting at 120 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 1 time, washing with ethanol for 1 time, and vacuum drying at 50 ℃ to obtain the Bi-MOF microspheres (Bi-MOF-M);
Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: ultrasonically dispersing 0.1g of Bi-MOF-M in 40mL of ethanol to obtain A; adding 0.1mmol of Na2MoO4·2H2Dissolving O in 20mL of glycol to obtain B, dropwise adding the B into A, stirring at room temperature for 1h, transferring to a hydrothermal reaction kettle, and dissolving in 1Reacting for 12h at 20 ℃, naturally cooling to room temperature after the reaction is finished, filtering, washing for 1 time by deionized water, washing for 1 time by ethanol, and vacuum drying at 50 ℃ to obtain the Bi-MOF-M/Bi2MoO6A visible light catalyst;
prepared Bi-MOF-M/Bi2MoO6The application of the visible light catalyst for treating methylene blue wastewater comprises the following steps:
at normal temperature, the prepared Bi-MOF-M/Bi2MoO6The visible light catalyst is added into 100mL methylene blue waste water sample with the concentration of 50mg/L, and the dosage is as follows: 0.5g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. And measuring the change of the absorbance of the methylene blue wastewater along with the illumination time by using an ultraviolet-visible spectrophotometry, and calculating the removal rate of the methylene blue. The results show that: the reaction was carried out for 35min, the removal rate was 95.3%.
Example 2
This example is Bi-MOF-M/Bi2MoO6Preparation and application of visible light catalyst. The specific process is as follows:
preparation of Bi-MOF microspheres (Bi-MOF-M): adding 5mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 5mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the obtained B into A, stirring at room temperature for 3h, then transferring to a hydrothermal reaction kettle, reacting at 160 ℃ for 18h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 80 ℃ to obtain the Bi-MOF microspheres (Bi-MOF-M);
Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: ultrasonically dispersing 0.3g of Bi-MOF-M in 40mL of ethanol to obtain A; adding 0.5mmol of Na2MoO4·2H2Dissolving O in 20mL of glycol to obtain B, dropwise adding the B into A, stirring at room temperature for 3h, transferring to a hydrothermal reaction kettle, reacting at 180 ℃ for 18h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 80 ℃ to obtain the Bi-MOF-M/Bi2MoO6A visible light catalyst;
prepared Bi-MOF-M/Bi2MoO6The application of the visible light catalyst for treating methyl orange wastewater comprises the following steps:
at normal temperature, the prepared Bi-MOF-M/Bi2MoO6Adding a visible light catalyst into 100mL of methyl orange wastewater sample with the concentration of 100mg/L, wherein the dosage is as follows: 1.0g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. And measuring the change of the absorbance of the methylene blue wastewater along with the illumination time by using an ultraviolet-visible spectrophotometry, and calculating the removal rate of the methyl orange. The results show that: the reaction was carried out for 35min, the removal rate was 97.8%.
Example 3
This example is Bi-MOF-M/Bi2MoO6Preparation and application of visible light catalyst. The specific process is as follows:
preparation of Bi-MOF microspheres (Bi-MOF-M): 2mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 3mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the obtained B into A, stirring at room temperature for 2h, then transferring to a hydrothermal reaction kettle, reacting at 150 ℃ for 16h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 60 ℃ to obtain the Bi-MOF microspheres (Bi-MOF-M);
Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: ultrasonically dispersing 0.2g of Bi-MOF-M in 40mL of ethanol to obtain A; adding 0.3mmol of Na2MoO4·2H2Dissolving O in 20mL of glycol to obtain B, dropwise adding the B into A, stirring at room temperature for 2h, transferring to a hydrothermal reaction kettle, reacting at 160 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 60 ℃ to obtain the Bi-MOF-M/Bi2MoO6A visible light photocatalyst.
FIGS. 1 and 2 are Bi-MOF-M and Bi-MOF-M/Bi, respectively2MoO6SEM image of visible light catalystSee, chemical bonding type heterojunction photocatalyst Bi-MOF-M/Bi2MoO6After the surface layer is formed, the appearance is obviously changed, and the surface layer is changed into petal-shaped Bi from rod-shaped stacking2MoO6And (3) a layer. The resulting Bi-MOF-M/Bi2MoO6The visible light catalyst can effectively widen the absorption range of visible light and effectively improve the absorption intensity, thereby improving the visible light catalytic performance, as shown in figure 3, wherein 1 is Bi-MOF-M, and 2 is Bi-MOF-M/Bi2MoO6。
Prepared Bi-MOF-M/Bi2MoO6The application of the visible light catalyst for treating rhodamine B wastewater comprises the following steps:
at normal temperature, preparing Bi-MOF-M/Bi2MoO6The visible light photocatalyst is added into 100mL of rhodamine B waste water sample with the concentration of 80mg/L, and the dosage is as follows: 0.7g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. And measuring the change of the absorbance of the rhodamine B wastewater along with the illumination time by using an ultraviolet-visible spectrophotometry, and calculating the removal rate of the rhodamine B. The results show that: the reaction was carried out for 35min, with a removal rate of 96.8%.
Example 4
This example is Bi-MOF-M/Bi2MoO6Preparation and application of visible light catalyst. The specific process is as follows:
preparation of Bi-MOF microspheres (Bi-MOF-M): 3mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 4mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the obtained B into A, stirring at room temperature for 1.5h, then transferring to a hydrothermal reaction kettle, reacting at 130 ℃ for 15h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 1 time, washing with ethanol for 2 times, and vacuum-drying at 70 ℃ to obtain the Bi-MOF microspheres (Bi-MOF-M);
Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: ultrasonically dispersing 0.3g of Bi-MOF-M in 40mL of ethanol to obtain A; adding 0.4mmol of Na2MoO4·2H2Dissolving O in 20mL of ethylene glycol to obtain B, and dissolving the B in the obtained solutionB is dripped into A, stirred for 2h at room temperature, then transferred into a hydrothermal reaction kettle, reacted for 15h at 130 ℃, naturally cooled to room temperature after the reaction is finished, filtered, washed for 2 times by deionized water, washed for 1 time by ethanol, and dried in vacuum at 50 ℃ to obtain the Bi-MOF-M/Bi2MoO6A visible light catalyst;
prepared Bi-MOF-M/Bi2MoO6The application of the visible light catalyst for treating tetracycline hydrochloride wastewater comprises the following steps:
at normal temperature, the prepared Bi-MOF-M/Bi2MoO6The visible light photocatalyst is added into 100mL tetracycline hydrochloride waste water sample with the concentration of 60mg/L, and the dosage is as follows: 0.5g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. And measuring the change of the absorbance of the tetracycline hydrochloride wastewater along with the illumination time by using an ultraviolet-visible spectrophotometry, and calculating the removal rate of the tetracycline hydrochloride. The results show that: the reaction was carried out for 35min, and the removal rate was 93.5%.
Example 5
This example is Bi-MOF-M/Bi2MoO6Preparation and application of visible light catalyst. The specific process is as follows:
preparation of Bi-MOF microspheres (Bi-MOF-M): 2mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 4mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the obtained B into A, stirring at room temperature for 1h, then transferring to a hydrothermal reaction kettle, reacting at 140 ℃ for 17h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 1 time, and vacuum drying at 60 ℃ to obtain the Bi-MOF microspheres (Bi-MOF-M);
Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: ultrasonically dispersing 0.3g of Bi-MOF-M in 40mL of ethanol to obtain A; adding 0.2mmol of Na2MoO4·2H2Dissolving O in 20mL of glycol to obtain B, dropwise adding the B into A, stirring at room temperature for 2.5h, transferring to a hydrothermal reaction kettle, reacting at 150 ℃ for 13h, naturally cooling to room temperature after the reaction is finished, filtering, and removingWashing the seed water for 1 time, washing the seed water for 1 time by ethanol, and drying the seed water in vacuum at 70 ℃ to obtain the Bi-MOF-M/Bi2MoO6A visible light catalyst;
prepared Bi-MOF-M/Bi2MoO6The application of the visible light catalyst for treating the sulfamethazine wastewater comprises the following steps:
at normal temperature, the prepared Bi-MOF-M/Bi2MoO6The visible light catalyst is added into 100mL sulfamethazine waste water sample with the concentration of 60mg/L, and the dosage is as follows: 0.8g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. And measuring the change of the absorbance of the sulfamethazine wastewater along with the illumination time by using an ultraviolet-visible spectrophotometry, and calculating the removal rate of the sulfamethazine. The results show that: the reaction was carried out for 35min, the removal rate was 92.7%.
Example 6
This example is the Bi-MOF-M/Bi prepared in example 32MoO6The application of the visible-light-driven photocatalyst focuses on investigating the reusability and residue of the visible-light-driven photocatalyst. The specific process is as follows: taking 100mL of 80mg/L methylene blue solution and 100mL of 80mg/L tetracycline hydrochloride solution as test solutions, namely Bi-MOF-M/Bi2MoO6The addition amount of the visible light catalyst is as follows: 0.8g/L, using a 300W xenon lamp as a light source, filtering out ultraviolet light by using a filter, and using visible light with the wavelength of more than 400nm as the light source. After illumination for 35min, the catalyst was separated by filtration, the removal rate of methylene blue and tetracycline hydrochloride was determined by ultraviolet-visible spectrophotometry, and the metal residue was determined by atomic absorption spectroscopy, the results of which are shown in FIG. 4. As can be seen from fig. 4: Bi-MOF-M/Bi prepared by the invention2MoO6The visible light catalyst is repeatedly used for 26 times, the performance is basically kept unchanged, and the residue of metal in a wastewater sample is not detected for 26 times, so that the visible light catalyst prepared by the invention has stable property and high efficiency, can be conveniently recycled by filtration, and greatly reduces the cost.
Bi-MOF-M/Bi prepared by the invention2MoO6The visible light catalyst can efficiently utilize visible light and degrade high-concentration organic pollutionThe catalyst has high efficiency, can reach a removal rate of more than 90% in 35min for various common refractory dye wastewater and high-concentration antibiotic wastewater, and has the advantages of stable performance, no residue, easy recovery and recycling.
Comparative example 1
Bi-MOF microspheres (Bi-MOF-M) are prepared in the manner of example 3, and rhodamine B wastewater is treated according to the method. The results show that: the reaction was carried out for 35min, the removal rate was 25.3%.
Comparative example 2
Impregnation method of Bi-MOF-M/Bi2MoO6Preparation of the composite photocatalyst and photocatalytic performance thereof.
Bi2MoO6The preparation of (1): adding Bi (NO)3)3·5H2O (3.480mmol) and Na2MoO4·2H2O (1.740mmol) was dispersed in 10mL of ethylene glycol and dissolved with vigorous stirring. Mixing the obtained Na2MoO4·2H2Slowly dripping O solution into the obtained Bi (NO)3)3·5H2And (4) adding the mixture into the O solution to obtain a mixed solution. Then, 20mL of ethanol was added dropwise to the above mixed solution, and the above mixed solution was transferred to a 50mL polytetrafluoroethylene-lined autoclave and left in an oven at 160 ℃ for 20 hours. Washing the prepared precipitate with deionized water and ethanol for several times, and vacuum drying at 60 deg.C for 24 hr to obtain Bi2MoO6。
Preparation of Bi-MOF-M/Bi by impregnation method2MoO6The composite photocatalyst comprises: 0.20g of Bi-MOF-M microspheres prepared in the manner of example 3 and 0.18g of Bi from comparative example 2 were admixed2MoO6Added to a 100mL beaker, then 15mL of ethanol was added to the beaker, covered with a preservative film to prevent evaporation of the ethanol and dust from falling into the beaker. After continuously stirring for 12 hours, putting the product into an oven at 60 ℃ for drying for 12 hours to obtain the Bi-MOF-M/Bi by the impregnation method2MoO6A composite photocatalyst is provided. Rhodamine B wastewater was treated in the manner of example 3. The results show that: the reaction was carried out for 35min, the removal rate was 36.7%.
Comparative example 3
Rod-like Bi-preparation of MOF: 2mmol of Bi (NO)3)3·5H2Dissolving O in 40mLN, N-dimethylformamide to obtain A; dissolving 3mmol of terephthalic acid in 30mLN, N-dimethylformamide to obtain B, dropwise adding the B into the A, stirring at room temperature for 2h, then transferring to a hydrothermal reaction kettle, reacting at 150 ℃ for 16h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 60 ℃ to obtain the rod-shaped Bi-MOF, wherein an SEM picture of the rod-shaped Bi-MOF is shown in figure 5; rhodamine B wastewater was treated as in example 3. The results show that: the reaction was carried out for 35min, the removal rate was 13.3%.
Comparative example 4
Preparing dumbbell-shaped bouquet Bi-MOF: 2mmol of Bi (NO)3)3·5H2Dissolving O in 40mL of glycol to obtain A; dissolving 3mmol of terephthalic acid in 30mL of ethylene glycol to obtain B, dropwise adding the B into the A, stirring at room temperature for 2h, then transferring to a hydrothermal reaction kettle, reacting at 150 ℃ for 16h, naturally cooling to room temperature after the reaction is finished, filtering, washing with deionized water for 2 times, washing with ethanol for 2 times, and vacuum drying at 60 ℃ to obtain the dumbbell-shaped flower bunch Bi-MOF, wherein an SEM picture is shown in FIG. 6; rhodamine B wastewater was treated as in example 3. The results show that: the reaction was carried out for 35min, the removal rate was 17.8%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (4)

1. Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6The preparation method of the visible light photocatalyst is characterized by comprising the following steps:
(1) preparation of Bi-MOF microspheres Bi-MOF-M: respectively dissolving a bismuth source and terephthalic acid in ethylene glycol and N, N-dimethylformamide to obtain solution A and solution B, dropwise adding the solution B into the solution A, stirring for 1-3 h, transferring to a hydrothermal reaction kettle, reacting at 120-160 ℃ for 12-18 h, cooling after the reaction is finished, carrying out solid-liquid separation, washing with water and ethanol for several times respectively, and drying to obtain a Bi-MOF microsphere Bi-MOF-M;
(2)Bi-MOF-M/Bi2MoO6preparation of visible light photocatalyst: dispersing the Bi-MOF-M prepared in the step (1) in ethanol to obtain a solution C, dissolving molybdate in ethylene glycol to obtain a solution D, dropwise adding the obtained solution D into the solution C, stirring for 1-3 h, transferring to a hydrothermal reaction kettle, reacting at 120-180 ℃ for 12-18 h, cooling after the reaction is finished, carrying out solid-liquid separation, washing with water and ethanol for several times respectively, and drying to obtain the Bi-MOF-M/Bi2MoO6A visible light photocatalyst;
the concentration of the bismuth source in the solution A is 0.025-0.125 mmol/mL; the concentration of the terephthalic acid in the solution B is 0.03-0.17 mmol/mL;
the molar ratio of the bismuth source to the terephthalic acid is 1-5: 1-5;
the content of Bi-MOF-M in the solution C is 2.5-7.5 mg/mL;
the concentration of molybdate in the solution D is 0.005-0.025 mmol/mL;
the mass molar ratio of the Bi-MOF-M to the molybdate is 1-3: 1-5 g/mmol.
2. Bi-MOF-M/Bi prepared by the preparation method of claim 12MoO6A visible light photocatalyst.
3. The Bi-MOF-M/Bi of claim 22MoO6The application of visible light catalyst in treating organic waste water.
4. Use according to claim 3, wherein the organic waste water comprises organic dye waste water and antibiotic waste water.
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