CN115999587A - Photocatalytic material and preparation method and application thereof - Google Patents
Photocatalytic material and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a photocatalytic material, a preparation method and application thereof, and belongs to the technical field of photocatalysis. The invention uses Bi 7 O 5 F 11 BiOF heterojunction as photocatalytic material by defining Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And BiOF is 7:1 to 1:1 in mass ratio, within this range, bi 7 O 5 F 11 The electric field in the/BiOF heterojunction interface can effectively separate electron hole pairs, prolong the separation state of photo-generated electrons, thereby more fully exerting the oxidation-reduction capability of the electron hole pairs, improving the catalytic activity of the photocatalyst, further being applicable to the treatment of organic wastewater, in particular being capable of being highEffectively degrading the perfluorinated compounds in the organic wastewater.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a photocatalysis material and a preparation method and application thereof.
Background
Perfluoroalkyl and polyfluoroalkyl materials (PFAS) have been widely used in a variety of industries and businesses over the past decades, causing serious environmental pollution problems. Among the wide variety of PFAS, the ecotoxicity and human health studies of perfluorooctyl sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are of great interest. And, since PFAS has a high bond energy C-F bond, it has excellent thermal and chemical stability, so that the conventional water treatment process cannot effectively remove it. Therefore, developing techniques to efficiently remove PFAS from water to protect human health is very challenging.
There are various methods to remove or degrade PFAS in water. Among them, the photocatalytic method has the advantages of simple operation, high oxidation efficiency and good environmental compatibility, and is concerned by researchers, and many researchers also try to develop various efficient photocatalysts for removing or degrading PFAS in water. Among the numerous photocatalytic materials, bismuth oxyhalides (bisx, x= F, cl, br, I) are due to their unique two-dimensional layered structure and tunable energy bands, as well as halogen layers and [ Bi 2 O 2 ] 2+ The internal electric field between the layers can accelerate charge migration and separation and thus exhibit attractive properties in PFAS degradation. For example, chinese patent CN201910153880.9 discloses a preparation method of bismuth oxyiodide heterojunction photocatalytic material, which controls the crystal phase structure of bismuth oxyiodide heterojunction by controlling the calcination temperature, so as to improve the catalytic activity of the photocatalytic material, and when the concentration of PFOA in the original wastewater is 15mg/L, the degradation rate of 6h reaches 81.3%.
However, although the existing bismuth oxyhalide can be used for degrading PFAS in wastewater, the efficiency of degrading PFAS in wastewater is limited, because the general bismuth oxyhalide has the defect of easy recombination of photo-generated electrons and holes, and the utilization ratio of electron holes is greatly reduced, so that PFAS pollutants such as PFOA in wastewater cannot be effectively degraded.
Disclosure of Invention
The invention aims to provide a photocatalytic material capable of efficiently catalyzing.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a photocatalytic material, which is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And the mass ratio of BiOF is 7:1-1:1.
Preferably, the Bi 7 O 5 F 11 And the mass ratio of BiOF is 7:1-2:1.
The invention also provides a preparation method of the photocatalytic material, which comprises the following steps:
(1) Mixing soluble bismuth salt with ethylene glycol to obtain a solution A;
(2) NH is added to 4 F. Mixing water and ethylene glycol to obtain a solution B;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 1:1-3:17;
(4) Carrying out hydrothermal reaction on the mixed solution obtained in the step (3) to obtain a photocatalytic material;
the step (1) and the step (2) are not time-sequential.
Preferably, the soluble bismuth salt in step (1) comprises bismuth nitrate.
Preferably, the ratio of the amount of soluble bismuth salt to the amount of ethylene glycol material in step (1) is 1:175.
Preferably, the soluble bismuth salt in step (1) and the NH in step (2) 4 The ratio of the amounts of the substances of F is 1:1 to 1.2:1.
Preferably, NH in step (2) 4 The concentration of F in the solution B is 0.1-0.12 mol/L.
Preferably, the rate of the dropping in the step (3) is 1 drop/s.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 150-170 ℃; the heat preservation time of the hydrothermal reaction is 20-24 h.
The invention also provides an application of the photocatalytic material according to the technical scheme or the photocatalytic material prepared by any one of the preparation methods in treating organic wastewater.
The invention provides a photocatalytic material, which is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And the mass ratio of BiOF is 7:1-1:1. In the present invention, bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And BiOF is 7:1 to 1:1 in mass ratio, within this range, bi 7 O 5 F 11 The electric field in the/BiOF heterojunction interface can effectively separate electron hole pairs, and prolong the separation state of photo-generated electrons, so that the redox capacity of the electron hole pairs is fully exerted, the catalytic activity of the photocatalyst is improved, and the method can be applied to treating organic wastewater, and particularly can be used for efficiently degrading perfluorinated compounds in the organic wastewater. Example results show that Bi in the photocatalytic material provided by the invention 7 O 5 F 11 And BiOF is 7:1, the Bi obtained 7 O 5 F 11 The BiOF heterojunction photocatalyst has the best performance, and the degradation rate of PFOA of 15mg/L can reach 100% under the irradiation of ultraviolet light of 60 min.
Drawings
FIG. 1 is an XRD pattern of photocatalytic materials prepared in examples 1 to 5 and comparative examples 1 to 2 according to the present invention;
FIG. 2 is an SEM image of the photocatalytic materials prepared in examples 1 to 5 and comparative examples 1 to 2 according to the present invention;
wherein BiF-1, biF-2, biF-3, biF-4 and BiF-5 are the abbreviations of the photocatalytic materials prepared in examples 1 to 5 in this order;
FIG. 3 is a graph showing the catalytic performance test of the photocatalytic materials prepared in examples 1 to 5 and comparative examples 1 to 2 according to the present invention;
FIG. 4 is a graph showing the catalytic performance test of the photocatalytic material prepared in example 2 of the present invention.
Detailed Description
The invention provides a photocatalytic material, which is Bi 7 O 5 F 11 BiOF heterojunction.
In the present invention, the Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 7:1 to 1:1, preferably 7:1 to 2:1, and in embodiments may be specifically 7:1, 6:1, 5:1, 4:1, 3:1 or 2:1. The invention uses Bi 7 O 5 F 11 BiOF heterojunction as photocatalytic material by defining Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 When the mass ratio of BiOF is within the above range, bi is 7 O 5 F 11 The electric field in the/BiOF heterojunction interface can effectively separate electron hole pairs, and prolong the separation state of photo-generated electrons, so that the redox capacity of the electron hole pairs is fully exerted, the catalytic activity of the photocatalyst is improved, and the perfluorinated compounds can be efficiently degraded.
The invention also provides a preparation method of the photocatalytic material, which comprises the following steps:
(1) Mixing soluble bismuth salt with ethylene glycol to obtain a solution A;
(2) NH is added to 4 F. Mixing water and ethylene glycol to obtain a solution B;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 1:1-3:17;
(4) Carrying out hydrothermal reaction on the mixed solution obtained in the step (3) to obtain a photocatalytic material;
the step (1) and the step (2) are not time-sequential.
The invention mixes soluble bismuth salt with glycol to obtain solution A. The source of ethylene glycol is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the ethylene glycol is capable of reacting with a portion of Bi ions to form an alkoxide on the one hand; on the other hand, glycol is used as a solvent for dissolving the soluble bismuth salt, and because the glycol has certain viscosity, in the hydrothermal process taking the glycol as the solvent, the larger viscosity of the glycol can prevent the growth process of the material under the action of the hydrothermal; in addition, ethylene glycol can act as a growth template for the bisx under hydrogen bonding.
In the present invention, the soluble bismuth salt preferably includes bismuth nitrate, more preferably Bi (NO 3 ) 3 ·5H 2 O. The invention provides a bismuth source for the photocatalytic material by selecting the soluble bismuth salt.
In the present invention, the ratio of the amount of the soluble bismuth salt to the amount of the substance of ethylene glycol is preferably 1:175. The present invention can sufficiently dissolve the soluble bismuth salt in ethylene glycol by controlling the ratio of the amounts of the soluble bismuth salt and the ethylene glycol within the above range.
The method of mixing the soluble bismuth salt with ethylene glycol is not particularly limited, and the soluble bismuth salt may be completely dissolved in ethylene glycol by a mixing method well known to those skilled in the art. In the present invention, the mixing of the soluble bismuth salt with ethylene glycol is preferably performed under ultrasound. The invention has no special limitation on the power and time of the ultrasonic wave, and can completely dissolve the soluble bismuth salt in glycol.
The invention uses NH 4 F. Water and ethylene glycol to give solution B. In the present invention, the solvent of the solution B is a mixed solution of pure water and ethylene glycol, and the volume ratio of water to ethylene glycol in the solution B is preferably 9:1 to 3:7, more preferably 9:1 to 1:1, and in embodiments, the volume ratio of water to ethylene glycol may be specifically 9:1, 7:3, 1:1 or 3:7. In the invention, the solution B comprises water, the content of water in the mixed solution is regulated by regulating the volume ratio of the water to the glycol in the solution B, and the regulation and control of Bi are realized by regulating the volume ratio of the water to the glycol in the mixed solution 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And the mass ratio of BiOF, thereby regulating and controlling Bi 7 O 5 F 11 Morphology and band structure of the/BiOF heterojunction.
In the present invention, the NH is 4 The concentration of F in the solution B is preferably 0.1 to 0.12mol/L, more preferably 0.1mol/L. In the present invention, the NH is 4 F concentration in solution B isWhen the amount is within the above range, the reaction can be sufficiently carried out.
In the present invention, the soluble bismuth salt and the NH 4 The ratio of the amounts of the substances of F is preferably 1:1 to 1.2:1, more preferably 1:1 to 1.1:1. In the present invention, the NH is 4 F can react with Bi ions to finally form Bi 7 O 5 F 11 BiOF heterojunction when the soluble bismuth salt is mixed with the NH 4 When the ratio of the amount of F is within the above range, the soluble bismuth salt can be reacted sufficiently to form Bi 7 O 5 F 11 BiOF heterojunction.
The invention is to the NH 4 F. The method of mixing water and ethylene glycol is not particularly limited, and NH can be obtained by mixing methods known to those skilled in the art 4 F is completely dissolved. In the present invention, the NH is 4 F. The mixing of water and ethylene glycol is preferably carried out under ultrasound. The invention has no special limitation on the power and time of the ultrasonic wave, and can completely dissolve the soluble bismuth salt in glycol.
In the invention, the time sequence of obtaining the solution A and the solution B is not sequential.
After obtaining solution A and solution B, the invention adds the solution B into the solution A in a dropwise manner.
In the invention, the volume ratio of water to glycol in the mixed solution is 1:1-3:17, preferably 1:1-1:3. In the invention, because the solvent of the solution A is glycol, the solution B comprises water and glycol, and the solution B is dropwise added into the solution A to enable water to exist in the system, when the water exists in the reaction system, part of Bi ions and glycol react to generate alkoxide, and the rest of Bi ions are hydrolyzed to form BiONO 3 The method comprises the steps of carrying out a first treatment on the surface of the At NH 4 Bi ions and NH in the presence of F 4 F has stronger coordination and forms a diamine complex. Therefore, the invention realizes the regulation and control of Bi by adjusting the volume ratio of water and glycol in the mixed solution 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And the mass ratio of BiOF, thereby regulating and controlling Bi 7 O 5 F 11 BiOF heterojunction tableOxygen defects and morphology of the facets.
In the present invention, when the volume ratio of water and ethylene glycol in the mixed solution is in the above range, bi can be caused 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And BiOF in a mass ratio of 7:1 to 1:1 to obtain Bi 7 O 5 F 11 The electric field in the/BiOF heterojunction interface can effectively separate electron hole pairs, prolong the separation state of photo-generated electrons, thereby more fully playing the oxidation-reduction capability of the electron hole pairs and improving the catalytic activity of the photocatalyst.
In the present invention, since electron transfer from the photocatalyst to the contaminant is involved in the photocatalytic decomposition process, the morphology of the photocatalyst is considered to play an important role in improving the decomposition rate. When the volume ratio of water and glycol in the mixed solution is in the above range, the morphology of the photocatalytic material changes with the change of the volume ratio of water and glycol in the mixed solution. When the volume ratio of water to glycol in the mixed solution is 1:1, the photocatalytic material mainly takes the agglomerated granular morphology as a main part, and the particle size is about 50 nm; when the volume ratio of water to glycol in the mixed solution is 9:11, the photocatalytic material mainly takes a sheet-shaped structure with the thickness of about 100nm as a main part; when the volume ratio of water to glycol in the mixed solution is 3:17-7:13, the photocatalytic material is mainly stacked in a regular hexagonal sheet structure. In the invention, the morphology of the photocatalytic material is regulated by regulating the specific energy of the volume of water and glycol in the mixed solution, so that the photocatalyst promotes the electron transfer from the photocatalyst to pollutants during application, and the activity of the photocatalytic material is improved.
In the present invention, the rate of the dropping is preferably 1 to 2 drops/s. In the present invention, when the rate of the dropping is within the above range, the rate of hydrolysis reaction of the soluble bismuth salt with water can be controlled to prevent Bi from being formed 7 O 5 F 11 BiOF heterojunction.
In the present invention, the dropping of the solution B to the solution a is preferably performed under stirring. In the present invention, the stirring can bring the solution a into sufficient contact with the solution B to promote the hydrolysis of the soluble bismuth salt. The stirring time is not particularly limited, and the stirring time can be adjusted according to experimental requirements. In the present invention, the stirring time is preferably 30 minutes after the completion of the dropping, and the solution A and the solution B are brought into sufficient contact to obtain a mixed solution.
After the mixed solution is obtained, the mixed solution is subjected to hydrothermal reaction to obtain the photocatalytic material.
In the present invention, the temperature of the hydrothermal reaction is preferably 150 to 170 ℃, more preferably 160 to 170 ℃; the time of the hydrothermal reaction is preferably 20 to 24 hours, more preferably 22 to 24 hours. The temperature rising rate of the hydrothermal reaction temperature is not particularly limited, and the hydrothermal reaction temperature may be reached. In the present invention, a part of Bi ions react with ethylene glycol to form alkoxide, and the remaining part of Bi ions are hydrolyzed to form BiONO 3 The method comprises the steps of carrying out a first treatment on the surface of the At NH 4 Bi ions and NH in the presence of F 4 F forms a diamine complex, and the coordination complex gradually releases Bi ions during the hydrothermal reaction, wherein the Bi ions and F - Reaction to form BiF 3 Localized BiF 3 Is accumulated to form Bi 7 O 5 F 11 . Meanwhile, in the hydrothermal process, the high viscosity of the ethylene glycol can also prevent the growth process of the material under the action of the hydrothermal, the ethylene glycol with a long-chain structure under the action of hydrogen bonds can also be used as a growth template of the BiOX, and the BiOX forms a microsphere structure through the self-assembly process. In the present invention, when the temperature and time of the hydrothermal reaction are within the above ranges, the reaction can be sufficiently carried out to form Bi 7 O 5 F 11 BiOF heterojunction.
The apparatus for the hydrothermal reaction is not particularly limited, and a hydrothermal reaction apparatus known to those skilled in the art may be used. In the present invention, the apparatus for hydrothermal reaction is preferably a reaction vessel.
After the hydrothermal reaction is completed, the system obtained after the hydrothermal reaction is preferably subjected to cooling, solid-liquid separation, solid washing and drying in sequence. In the present invention, the cooling can reduce the operating temperature; the solid-liquid separation and solid washing can remove impurities on the surface of the material; the drying is capable of removing the residual reagent from the surface of the solid material. The method of the present invention is not particularly limited, and the method of the cooling, solid-liquid separation, solid washing and drying may be any method known to those skilled in the art. In the present invention, the cooled temperature is preferably cooled to room temperature; the solid-liquid separation is preferably centrifugation; the washing is preferably carried out by washing with pure water for three times and then washing with pure ethanol for three times; the temperature of the drying is preferably 80 ℃.
The preparation method provided by the invention comprises the steps of mixing soluble bismuth salt with ethylene glycol to obtain a solution A; NH is added to 4 F. Mixing water and ethylene glycol to obtain a solution B; the volume ratio of the water to the glycol is 9:1-3:7; dropwise adding the step solution B into the solution A to obtain a mixed solution; and carrying out hydrothermal reaction on the mixed solution to obtain the photocatalytic material. The invention controls the water content in the system by controlling the volume ratio of water and glycol, thereby controlling Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of bisof.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 7:1.
The preparation method of the photocatalytic material comprises the following steps:
(1) 2mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O and 20mL of glycol for 30min to obtain a solution A;
wherein: bi (NO) 3 ) 3 ·5H 2 The ratio of O to the amount of ethylene glycol material was 1:175;
(2) 2mmol of NH 4 F, carrying out ultrasonic treatment on the solution with 20mL of pure water for 30min, and uniformly mixing to obtain a solution B;
wherein: the solvent of the solution B is pure water;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) at a rate of 1 drop/s under stirring, and continuing stirring for 30min to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 1:1;
(4) And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (3) in a reaction kettle, wherein the temperature of the hydrothermal reaction is 160 ℃ and the time is 24 hours, cooling the reaction kettle to about 25 ℃, taking out the material in the reaction kettle, centrifugally separating, washing with pure water for three times, washing with pure ethanol for three times, and then drying in an oven at 80 ℃ to obtain the photocatalytic material, hereinafter called BiF-1.
Example 2
A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 3:1.
The preparation method of the photocatalytic material comprises the following steps:
(1) 2mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O and 20mL of glycol for 30min to obtain a solution A;
wherein: bi (NO) 3 ) 3 ·5H 2 The ratio of O to the amount of ethylene glycol material was 1:175;
(2) 2mmol of NH 4 F. Carrying out ultrasonic treatment on 18mL of water and 2mL of glycol for 30min, and uniformly mixing to obtain a solution B;
wherein: the volume ratio of water to glycol is 9:1;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) at a rate of 1 drop/s under stirring, and continuing stirring for 30min to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 9:11;
(4) And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (3) in a reaction kettle, wherein the temperature of the hydrothermal reaction is 160 ℃ and the time is 24 hours, cooling the reaction kettle to about 25 ℃, taking out materials in the reaction kettle, centrifugally separating, washing with pure water for three times, washing with pure ethanol for three times, and then drying in an oven at 80 ℃ to obtain the photocatalytic material, hereinafter called BiF-2.
Example 3
A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 2:1.
The preparation method of the photocatalytic material comprises the following steps:
(1) 2mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O and 20mL of glycol for 30min to obtain a solution A;
wherein: bi (NO) 3 ) 3 ·5H 2 The ratio of O to the amount of ethylene glycol material was 1:175;
(2) 2mmol of NH 4 F. Carrying out ultrasonic treatment on 14mL of water and 6mL of glycol for 30min, and uniformly mixing to obtain a solution B;
wherein: the volume ratio of water to glycol is 7:3;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) at a rate of 1 drop/s under stirring, and continuing stirring for 30min to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 7:13;
(4) And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (3) in a reaction kettle, wherein the temperature of the hydrothermal reaction is 160 ℃ and the time is 24 hours, cooling the reaction kettle to about 25 ℃, taking out the material in the reaction kettle, centrifugally separating, washing with pure water for three times, washing with pure ethanol for three times, and then drying in an oven at 80 ℃ to obtain the photocatalytic material, hereinafter called BiF-3.
Example 4
A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 2:1.
The preparation method of the photocatalytic material comprises the following steps:
(1) 2mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O and 20mL of glycol for 30min to obtain a solution A;
wherein: bi (NO) 3 ) 3 ·5H 2 The ratio of O to the amount of ethylene glycol material was 1:175;
(2) 2mmol of NH 4 F. Carrying out ultrasonic treatment on 10mL of water and 10mL of glycol for 30min, and uniformly mixing to obtain a solution B;
wherein: the volume ratio of water to glycol is 1:1;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) at a rate of 1 drop/s under stirring, and continuing stirring for 30min to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 1:3;
(4) And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (3) in a reaction kettle, wherein the temperature of the hydrothermal reaction is 160 ℃ and the time is 24 hours, cooling the reaction kettle to about 25 ℃, taking out the material in the reaction kettle, centrifugally separating, washing with pure water for three times, washing with pure ethanol for three times, and then drying in an oven at 80 ℃ to obtain the photocatalytic material, hereinafter called BiF-4.
Example 5
A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And a mass ratio of BiOF of 1:1.
The preparation method of the photocatalytic material comprises the following steps:
(1) 2mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O and 20mL of glycol for 30min to obtain a solution A;
wherein: bi (NO) 3 ) 3 ·5H 2 The ratio of O to the amount of ethylene glycol material was 1:175;
(2) 2mmol of NH 4 F. 6mL of water and 14mL of glycol are treated by ultrasonic treatment for 30min and are uniformly mixed to obtain a solution B;
wherein: the volume ratio of water to glycol is 3:7;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) at a rate of 1 drop/s under stirring, and continuing stirring for 30min to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 3:17;
(4) And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (3) in a reaction kettle, wherein the temperature of the hydrothermal reaction is 160 ℃ and the time is 24 hours, cooling the reaction kettle to about 25 ℃, taking out the material in the reaction kettle, centrifugally separating, washing with pure water for three times, washing with pure ethanol for three times, and then drying in an oven at 80 ℃ to obtain the photocatalytic material, hereinafter called BiF-5.
Test example 1
The photocatalytic materials prepared in examples 1 to 5 and comparative examples 1 to 2 were tested using an X-ray diffractometer, and the obtained XRD patterns are shown in fig. 1.
As can be seen from FIG. 1, the photocatalytic materials prepared in examples 1 to 5 have diffraction peaks of 15.49 °, 22.31 °, 24.69 °, 26.67 °, 29.26 °, 31.27 °, 34.88 ° in terms of 2θ, respectively, with Bi 7 O 5 F 11 Is numbered 97-016-7074
(202) (112), (401), (402), (113) faces; the diffraction peaks belonging to BiOF correspond to the (001), (101), (110), (102), (112), (200), (211) surfaces of standard card No.97-020-1620 one by one, which also confirms that the photocatalytic materials prepared in examples 1 to 5 have the structure Bi 7 O 5 F 11 BiOF heterojunction.
Test example 2
The photocatalytic materials prepared in examples 1 to 5 were tested by using a scanning electron microscope, and SEM images obtained are shown in fig. 2.
From FIG. 2, it can be seen that, from FIG. 2, biF-1 mainly takes the form of agglomerated particles, and the particle size is about 50 nm; the BiF-2 photocatalyst is mainly in a flaky structure of about 100 nm; with the increase of the ethylene glycol content in the system, the prepared BiF-3 to BiF-5 are mainly stacked in a regular hexagonal sheet structure. This shows that the volume ratio of water to glycol in solution B has a great influence on the microscopic morphology of the photocatalytic material when the volume ratio of water to glycol is different, and the volume ratio of water to glycol not only affects Bi in the composite material 7 O 5 The mass ratio of F11 to BiOF also greatly alters the microscopic morphological characteristics of the material.
Test example 3
Preparing PFOA aqueous solution with concentration of 15mg/L by deionized water, taking 40mL, adding into a 50mL quartz tube equipped with a photoreaction instrument, and then preparing the photocatalytic materials in examples 1-5 to make the concentration of the photocatalytic materials in the PFOA aqueous solution be 0.1 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the For comparison, another 40mL of PFOA aqueous solution having a concentration of 15mg/L was added to a 50mL quartz tube equipped with a photoreactor, and commercial TiO was added thereto 2 The concentration of the photocatalytic material in the PFOA aqueous solution is 0.1 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The condensed water is turned on to control the reaction temperature to 25 ℃, the dark reaction is firstly carried out under the action of stirring, the adsorption and desorption balance is achieved when the concentration of PFOA in the PFOA aqueous solution is not changed, then a light source wavelength peak value is turned on to 365nm, the lamp power is 500W mercury lamp, the concentration of PFOA before and after the reaction is measured by a high performance liquid chromatography-mass spectrometry technology, and the catalytic performance test results of the photocatalytic materials prepared in examples 1-5 are shown in figure 3.
As can be seen from fig. 3, commercial TiO under the same photocatalytic degradation conditions 2 The PFOA removal rate after 2h illumination is about 23%. The photocatalytic material prepared by the invention has excellent photocatalytic performance in the PFOA degradation process, and the PFOA removal rate is ordered from high to low, and the photocatalytic material sequentially comprises the following components in sequence: biF-2>BiF-1>BiF-3>BiF-4>BiF-5, because the invention regulates and controls Bi by controlling the volume ratio of water and glycol in the mixed solution 7 O 5 F 11 /BiOFBi in heterojunction 7 O 5 F 11 And the mass ratio of BiOF, so that the morphology and the surface oxygen defect of the photocatalytic material are changed, and further different and excellent photocatalytic performances are shown for degrading PFOA in wastewater. Wherein, the photo-catalytic performance of BiF-2 is optimal, and the PFOA of 15mg/L can be degraded under the irradiation of ultraviolet light of 60 min. The In-MOF/BiOF photocatalyst reported by (Insights into highly efficient photodegradation of poly/perfluoroalkyl substances by In-MOF/BiOF heterojunctions: building-In electric field and strong surface adsorption Applied Catalysis B: environmental 304 (2022) 121013) was used for degrading PFOA, and the degradation rate of 150min only reached 100% at an initial concentration of 15 mg/L. This means Bi 7 O 5 F 11 The BiOF heterojunction photocatalyst has very good catalytic degradation performance on PFOA.
Test example 4
Preparing PFOA aqueous solution with concentration of 15mg/L by deionized water, taking 40mL, adding into a 50mL quartz tube equipped with a photoreaction instrument, and then adding the photocatalytic material prepared in example 2 to make the concentration of the photocatalytic material in the PFOA aqueous solution be 0.1 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the In addition, a 15mg/L PFOS aqueous solution was prepared, 40mL was taken and put into a 50mL quartz tube equipped with a photoreactor, and then the photocatalytic material prepared in example 2 was added so that the concentration of the photocatalytic material in the PFOS aqueous solution was 0.1 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The condensed water is turned on to control the reaction temperature to 25 ℃, the dark reaction is carried out under the action of stirring until the concentration of PFOA in the PFOA aqueous solution is no longer changed, the adsorption and desorption balance is achieved, then a lamp is turned on, the lamp power is 500W mercury lamp, the concentrations of PFOS and PFOA before and after the reaction are measured by a high performance liquid chromatography-mass spectrometry technology, and the catalytic performance test results of the photocatalytic materials prepared in examples 1 to 5 are shown in FIG. 4.
As can be seen from fig. 4, when the volume ratio of water and ethylene glycol in the solution B is 9:1, i.e., the volume ratio of water and ethylene glycol in the mixed solution is 9:11, the prepared Bi 7 O 5 F 11 The BiOF heterojunction photocatalyst has the best performance, and the degradation rate can reach 100% in 30min and 60min respectively, which shows that Bi 7 O 5 F 11 BiOF heterojunction lightThe catalyst not only can degrade PFOA with high efficiency, but also has ultra-high catalytic degradation performance for PFOS.
In conclusion, the photocatalytic material provided by the invention has excellent photocatalytic activity and can be used for efficiently degrading perfluorinated compounds.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A photocatalytic material is Bi 7 O 5 F 11 BiOF heterojunction, said Bi 7 O 5 F 11 Bi in a BiOF heterojunction 7 O 5 F 11 And the mass ratio of BiOF is 7:1-1:1.
2. The photocatalytic material of claim 1, wherein the Bi 7 O 5 F 11 And the mass ratio of BiOF is 7:1-2:1.
3. A method of preparing a photocatalytic material according to claim 1 or 2, comprising the steps of:
(1) Mixing soluble bismuth salt with ethylene glycol to obtain a solution A;
(2) NH is added to 4 F. Mixing water and ethylene glycol to obtain a solution B;
(3) Dropwise adding the solution B obtained in the step (2) into the solution A obtained in the step (1) to obtain a mixed solution; the volume ratio of water to glycol in the mixed solution is 1:1-3:17;
(4) Carrying out hydrothermal reaction on the mixed solution obtained in the step (3) to obtain a photocatalytic material;
the step (1) and the step (2) are not time-sequential.
4. A method of preparation according to claim 3, wherein the soluble bismuth salt in step (1) comprises bismuth nitrate.
5. A process according to claim 3, wherein the ratio of the amount of soluble bismuth salt to the amount of ethylene glycol material in step (1) is 1:175.
6. The method according to claim 3, wherein the soluble bismuth salt in the step (1) and the NH in the step (2) 4 The ratio of the amounts of the substances of F is 1:1 to 1.2:1.
7. The method according to claim 3, wherein NH in the step (2) 4 The concentration of F in the solution B is 0.1-0.12 mol/L.
8. The method according to claim 3 or 6, wherein the rate of dropping in the step (3) is 1 to 2 drops/s.
9. The method according to claim 3, wherein the hydrothermal reaction in the step (4) is carried out at a temperature of 150 to 170 ℃; the heat preservation time of the hydrothermal reaction is 20-24 h.
10. Use of the photocatalytic material according to claim 1 or 2 or the photocatalytic material prepared by the preparation method according to any one of claims 3 to 9 for treating organic wastewater.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070190414A1 (en) * | 2004-10-01 | 2007-08-16 | Rutgers, The State University | Bismuth oxyfluoride based nanocomposites as electrode materials |
| CN104801320A (en) * | 2015-05-07 | 2015-07-29 | 南京信息工程大学 | Bismuth oxyfluoride photocatalyst and preparing method of bismuth oxyfluoride photocatalyst |
| CN104998666A (en) * | 2015-08-10 | 2015-10-28 | 南京信息工程大学 | Method for preparing bowknot-shaped fluorine-oxygen-bismuth photocatalyst and application of catalyst |
| CN106311288A (en) * | 2016-07-26 | 2017-01-11 | 南京信息工程大学 | Simple preparation method of novel Bi7F11O5/BiOCl composite photocatalyst and photocatalytic performance of novel Bi7F11O5/BiOCl composite photocatalyst |
| CN111632611A (en) * | 2019-03-01 | 2020-09-08 | 南开大学 | Preparation method of bismuth oxyiodide heterojunction photocatalytic material for degrading perfluorinated compounds |
| CN111632610A (en) * | 2019-03-01 | 2020-09-08 | 南开大学 | BiOI capable of efficiently degrading perfluorinated compounds1-xFxSolid solution photocatalytic material and preparation method thereof |
| CN112371143A (en) * | 2020-12-02 | 2021-02-19 | 南开大学 | Preparation method of bismuth oxyfluoride photocatalytic material with controllable shape and defects for degrading perfluorinated compounds |
-
2023
- 2023-02-20 CN CN202310133009.9A patent/CN115999587A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070190414A1 (en) * | 2004-10-01 | 2007-08-16 | Rutgers, The State University | Bismuth oxyfluoride based nanocomposites as electrode materials |
| CN104801320A (en) * | 2015-05-07 | 2015-07-29 | 南京信息工程大学 | Bismuth oxyfluoride photocatalyst and preparing method of bismuth oxyfluoride photocatalyst |
| CN104998666A (en) * | 2015-08-10 | 2015-10-28 | 南京信息工程大学 | Method for preparing bowknot-shaped fluorine-oxygen-bismuth photocatalyst and application of catalyst |
| CN106311288A (en) * | 2016-07-26 | 2017-01-11 | 南京信息工程大学 | Simple preparation method of novel Bi7F11O5/BiOCl composite photocatalyst and photocatalytic performance of novel Bi7F11O5/BiOCl composite photocatalyst |
| CN111632611A (en) * | 2019-03-01 | 2020-09-08 | 南开大学 | Preparation method of bismuth oxyiodide heterojunction photocatalytic material for degrading perfluorinated compounds |
| CN111632610A (en) * | 2019-03-01 | 2020-09-08 | 南开大学 | BiOI capable of efficiently degrading perfluorinated compounds1-xFxSolid solution photocatalytic material and preparation method thereof |
| CN112371143A (en) * | 2020-12-02 | 2021-02-19 | 南开大学 | Preparation method of bismuth oxyfluoride photocatalytic material with controllable shape and defects for degrading perfluorinated compounds |
Non-Patent Citations (1)
| Title |
|---|
| MING REN等: "Influence of O/F ratio on oxygen defect and photochemical properties of BixOyFz", MATERIALS AND DESIGN, no. 131, 19 June 2017 (2017-06-19), pages 402 - 409 * |
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