CN115430462A - PVDF (polyvinylidene fluoride) membrane loaded Bi-based photocatalytic material as well as preparation method and application thereof - Google Patents

PVDF (polyvinylidene fluoride) membrane loaded Bi-based photocatalytic material as well as preparation method and application thereof Download PDF

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CN115430462A
CN115430462A CN202211064362.8A CN202211064362A CN115430462A CN 115430462 A CN115430462 A CN 115430462A CN 202211064362 A CN202211064362 A CN 202211064362A CN 115430462 A CN115430462 A CN 115430462A
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biocooh
solution
pvdf
photocatalytic material
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郑亚鸽
张良
王耀
钟吕玲
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Xian University of Architecture and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/39—
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention discloses a PVDF membrane loaded Bi-based photocatalytic material, a preparation method and application thereof 2 O 2 ] 2+ The quasi-fluorescent layer is formed by inserting formic acid. Then, bi metal is compounded on BiOCOOH, so that the compounding of photo-generated electron-hole pairs can be effectively improved by loading a Bi simple substance on the BiOCOOH, and the absorption intensity of visible light is improved. The invention uses PVDF andthe photocatalyst is combined with the preparation to obtain a novel porous hybrid membrane material so as to solve the problems of photocatalyst loss caused by difficult recovery of the photocatalyst and partial aggregation of the photocatalyst in the reaction process, thereby improving the degradation effect of ciprofloxacin in water.

Description

PVDF (polyvinylidene fluoride) membrane loaded Bi-based photocatalytic material as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a Bi-based photocatalytic material loaded by a PVDF (polyvinylidene fluoride) membrane, and a preparation method and application thereof.
Background
Water resources are the most important substances for human survival, but with the acceleration of the industrialization process, more and more water resources are polluted. Contamination of water is potentially dangerous to both human health and the environment; it has both direct and indirect damage to the health of all organisms. Unlike conventional water treatment methods such as chlorination, ozonation, biodegradation, and ultraviolet irradiation, advanced oxidation technology provides a safer, more natural water treatment method. However, such methods have many disadvantages, such as high investment, high maintenance cost, large consumption of chemical reagents, and environmental problems caused by wastewater treatment.
Among the advanced oxidation technologies, the photocatalytic technology has the characteristics of environmental protection, no secondary pollution, simple operation and quick reaction, and is one of the important ways for solving the water pollution.
The photocatalysis technology is to perform catalysis under the action of light, and mostly occurs on the surface of a semiconductor or some adsorbed reaction small molecules. When the illumination energy exceeds the band gap energy of a conductor or a semiconductor, electrons are excited to jump to a conduction band from a valence band, and the same number of holes exist in the valence band; the separated electron-hole can migrate to the surface of a conductor or a semiconductor, and the electron-hole is captured by an electron donor or an electron acceptor respectively to generate oxidation-reduction reaction, and finally, the photocatalysis reaction is realized.
The natural solar energy and the photocatalysis technology are utilized to remove pollutants and decompose hydrogen in water, so that the environmental pollution can be reduced, the problem of energy shortage can be solved, and the method has economic benefit. TiO since 1972 2 It has been reported that there have been many studies on photocatalysts, but there are also defects in photocatalysts such as narrow light absorption range, easy recombination of electron-hole, difficult recovery, partial aggregation, etc.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a Bi-based photocatalytic material loaded by a PVDF (polyvinylidene fluoride) film as well as a preparation method and an application thereof, so as to solve the problems that the photocatalyst is not easy to recover in the prior art, so that the activity of the photocatalyst is reduced, and the photocatalyst is partially aggregated in the reaction process, so that the utilization rate and the photocatalytic degradation effect of the catalyst are improved, and the degradation effect of ciprofloxacin in water is improved.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the preparation method of the Bi-based photocatalytic material loaded by the PVDF membrane comprises the following steps:
step 1, adding Bi (NO) 3 ) 3 ·5H 2 Dissolving O in a mixed solvent of DMF and water, adding glycerol after dissolving, stirring to obtain a clear solution A, carrying out solvothermal reaction on the clear solution A to obtain a reaction product B, washing the reaction product B, and drying to obtain BiOCOOH powder;
step 2, adding Bi (NO) 3 ) 3 ·5H 2 Dissolving O in ethylene glycol to obtain a solution C; adding BiOCOOH powder into the solution C to obtain a reaction solution D, heating the reaction solution D for reaction, and washing a reaction product to obtain a Bi/BiOCOOH nano composite material;
and 3, dissolving PVP in DMF to obtain a solution E, adding the Bi/BiOCOOH nano composite material into the solution E, uniformly stirring to obtain a mixed solution F, adding PVDF into the mixed solution F, stirring to form a film forming solution G, and preparing the film forming solution into a film shape to obtain the Bi-based photocatalytic material loaded by the PVDF film.
The invention is further improved in that:
preferably, in step 1, bi (NO) 3 ) 3 ·5H 2 The mixing ratio of O, DMF and glycerol is as follows: 4mmol:30mL of: 50mL.
Preferably, in the step 1, the solvothermal reaction temperature is 160 ℃ and the solvothermal reaction time is 24 hours.
Preferably, in step 2, bi (NO) is added 3 ) 3 ·5H 2 O accounts for 2 to 6 percent of the mass of the BiOCOOH powder.
Preferably, in the step 2, the reaction solution D is heated to the reaction temperature of 150-180 ℃ and the reaction time is 8h.
Preferably, in step 3, the mixing ratio of PVP and DMF is 0.3g: (7.26-8) mL.
Preferably, in the step 2, the Bi/BiOCOOH nano composite material is added into the solution E, and then the stirring temperature is 40-80 ℃, and the stirring time is 8-15 h.
Preferably, the addition amount of the Bi/BiOCOOH nano composite material is 1-7%.
The PVDF membrane loaded Bi-based photocatalytic material prepared by any one of the preparation methods comprises a PVDF membrane, wherein flower-shaped BiOCOOH is loaded on the PVDF membrane, and Bi nanoparticles are loaded on the BiOCOOH.
An application of the PVDF membrane loaded Bi-based photocatalytic material to the degradation of antibiotics in water.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a Bi-based photocatalytic material loaded by a PVDF (polyvinylidene fluoride) membrane, which comprises the steps of firstly preparing BiOCOOH, wherein the BiOCOOH is a layered double-base oxide and is prepared from [ Bi 2 O 2 ] 2+ The quasi-fluorescent layer is formed by inserting formic acid. Then Bi metal is compounded on BiOCOOH, semimetal bismuth is used as a direct plasma photocatalyst, and the direct plasma photocatalyst has proved to have good photocatalytic activity, and the Surface Plasma Resonance (SPR) effect of the direct plasma photocatalyst has special electronic characteristics, similar to noble metals. Therefore, the elementary substance Bi loaded on the BiOCOOH can effectively improve the recombination of photo-generated electron-hole pairs and improve the absorption intensity of visible light. However, since the small-particle composite nanomaterial is easily agglomerated, it is difficult to recover in practical applications, which affects the photocatalytic performance of the composite semiconductor material and the reusability of the photocatalyst. The PVDF film is combined with the small-particle photocatalyst so that the particle photocatalyst is no longer easily aggregated.
The invention also discloses a Bi-based photocatalytic material loaded by the PVDF membrane, and the catalytic material loads the Bi/BiOCOOH nano composite material on the PVDF membrane, so that the Bi/BiOCOOH nano composite catalytic material can fully play a catalytic role in water. SEM, TEM, XPS and XRD characterize the successful preparation of the photocatalytic composite membrane, BET characterizes the pore diameter and pore volume of the composite membrane, UV-Vis, EIS, PC and PL characterize the optical performance of the composite membrane, and EPR characterizes the active substances which mainly play a role. Through pH and inorganic anion research experiments, the optimal treatment conditions of the composite membrane are determined.
The invention also discloses a Bi-based photocatalytic material loaded by the PVDF membrane for treating antibiotics in water, wherein BiOCOOH can generate electronic transition under the irradiation of external light larger than Eg of BiOCOOH in the catalysis process, separated electrons can migrate to a conduction band, and a valence band can leave a hole with the number equal to that of the electrons. Electrons in the BiOCOOH conduction band can be rapidly transferred to the elementary substance Bi, so that the separation of electron-hole pairs is remarkably promoted. These separated electrons react with dissolved oxygen in the system to form O 2 - The free radical and the cavity can directly react with water in the system to generate OH free radical, the cavity can also oxidize the ciprofloxacin, and the ciprofloxacin is degraded due to the existence of the active substances.
Drawings
FIG. 1 is a microscopic topography of a material prepared according to the present invention;
wherein, the A picture is the SEM picture of BiOCOOH, and the B picture is the SEM picture of Bi/BiOCOOH; c is a scanning energy spectrum
The diagram D, the diagram E and the diagram F are mapping diagrams of Bi/BiOCOOH respectively;
FIG. 2 is a top and cross-sectional SEM image of 0%,1%,3%,5%,7% Bi/BiOCOOH/PVDF from Panel A-J;
wherein, the A picture-E picture is a top SEM picture of 0%,1%,3%,5%,7%, and the F picture-J picture is a cross-sectional SEM picture of 0%,1%,3%,5%, 7%;
FIG. 3 is an XPS, XRD and analytical chart of the present invention;
wherein, the A picture-D picture is an XPS picture of Bi/BiOCOOH/PVDF; pattern E is the XRD pattern of the different materials; f diagram-G diagram shows the nitrogen adsorption-desorption diagram and the pore size distribution diagram of Bi/BiOCOOH/PVDF.
Fig. 4 is an optical performance investigation diagram.
Wherein, the A picture is a UV-vis picture of different materials; b is a band gap diagram of different materials;
the C picture is a valence band spectrum of Bi/BiOCOOH/PVDF; graph D is a PL graph of different materials;
E-F are EIS and PC plots of different materials.
In FIG. 5, the diagram A and the diagram B are the best scale exploration; c, comparing the photodegradation effects of three different catalysts;
d picture-E picture is to investigate the effect of inorganic anions and pH on the photodegradation effect of Bi/BiOCOOH/PVDF.
Panels a and B in fig. 6 detect active species during a photocatalytic reaction. Panel C and D are Bi/BiOCOOH/PVDF reuse diagram;
FIG. 7 is a mechanism diagram.
Detailed Description
The steps of the present invention will be described in further detail below with reference to the accompanying drawings and specific examples.
The invention discloses a Bi-based photocatalytic material loaded by a PVDF (polyvinylidene fluoride) film as well as a preparation method and application thereof, wherein the preparation method of the photocatalytic material comprises the following steps:
step 1. Synthesis of BiOCOOH by Solvothermal Process
Adding Bi (NO) 3 ) 3 ·5H 2 O (4 mmol) (1.94 g) was dissolved in 20mL DMF and 10mL water with vigorous stirring. After dissolution, 50mL of glycerol (glycerin) was added to the above solution, and stirred uniformly so that after each substance was dissolved, the solution became clear to obtain a clear solution a. And pouring the obtained solution into an autoclave with the volume of 100mL, and carrying out solvothermal reaction at 160 ℃ for 24h to generate an initial product of BiOCOOH, thereby obtaining a reaction product B. After the reaction is finished, washing the collected reaction product B for 3 times by using deionized water and ethanol, finally transferring the reaction product B into an oven, and drying the reaction product B for 15 hours at the temperature of 60 ℃ to obtain BiOCOOH powder;
step 2. Synthesis of Bi/BiOCOOH
The Bi/BiOCOOH nano composite material is prepared by a simple solvothermal method, and the specific process is as follows:
adding Bi (NO) 3 ) 3 ·5H 2 O was dissolved ultrasonically in 65mL Ethylene Glycol (EG) to give solution C. Adding BiOCOOH powder into the solution CIn which Bi (NO) 3 ) 3 ·5H 2 The mass ratio of O in the BiOCOOH powder is 1-7%, the mixture is uniformly stirred after ultrasonic dispersion to obtain a reaction solution D, and the reaction solution D is heated for 8 hours in a reaction kettle at the temperature of 150-180 ℃. The obtained composite material is washed by deionized water and ethanol for 3 times and dried for 12 hours at 80 ℃. Preparing the Bi/BiOCOOH nano composite material. BiOCOOH in the composite material is composed of 3D flower-like microspheres with uniform size (FIG. 3A-B).
Synthesis of Bi/BiOCOOH/PVDF
Dissolving PVP (polyvinylpyrrolidone) powder in a DMF (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring to obtain a solution E; grinding a certain amount of catalyst Bi/BiOCOOH, putting the ground catalyst Bi/BiOCOOH into the solution E, and uniformly stirring to obtain a mixed solution F;
PVDF (polyvinyl fluoride) powder is dissolved in the mixed solution F and mechanically stirred for 8-15 h at the temperature of 40-80 ℃ to form a film forming solution G; degassing the solution for 12h at constant temperature to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, soaking the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until the formed film is used. After the film material is completely formed, the filter paper is used for absorbing excessive moisture and is placed in a freshness protection package for subsequent use. In this step, the total weight of PVP, DMF, bi/BiOCOOH and PVDF was 10g.
The method is used for preparing the Bi-based photocatalytic material loaded by the PVDF membrane, namely a novel porous hybrid membrane material. The material comprises a PVDF film, bi nanoparticles and flower-shaped BiOCOOH, and the specific structure is that flower-shaped BiOCOOH is loaded on the PVDF film, and Bi nanoparticles are loaded on the BiOCOOH.
TABLE 1 proportions of the respective materials in the preparation of thin-film catalysts of different masses
Figure BDA0003827581140000061
Comparative example
Dissolving 3g PVP (polyvinylpyrrolidone) powder in 8mL DMF (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring;
2.1g of PVDF (polyvinyl fluoride) powder are dissolved in the above solution and mechanically stirred at 50 ℃ for 12h to form a solution; degassing the solution at constant temperature for 12h to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, immersing the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until use. After the film material is completely formed, the filter paper is used for absorbing excessive moisture and is placed in a freshness protection package for subsequent use.
Example 1
Step 1, biOCOOH synthesis is carried out by solvothermal method
Adding Bi (NO) 3 ) 3 ·5H 2 O (4 mmol) (1.94 g) was dissolved in 20mL DMF and 10mL water with vigorous stirring. After dissolution, 50mL of glycerol (glycerin) was added to the above solution, and stirred uniformly so that the solution became clear after dissolution of each substance. The obtained solution was poured into an autoclave having a volume of 100mL, and after solvothermal reaction at 160 ℃ for 24h, the initial product of BiOCOOH was produced. After the reaction is finished, washing the collected product for 3 times by using deionized water and ethanol, finally transferring the product into an oven, and drying the product for 15 hours at 60 ℃ to obtain BiOCOOH powder;
step 2. Synthesis of Bi/BiOCOOH
The Bi/BiOCOOH nano composite material is prepared by a simple solvothermal method, and the specific process is as follows:
0.021g Bi(NO 3 ) 3 ·5H 2 o was dissolved ultrasonically in 65mL Ethylene Glycol (EG). 0.42g of BiOCOOH powder is then added to the above solution, in which Bi (NO) is present 3 ) 3 ·5H 2 The mass ratio of O in the BiOCOOH powder is 5%, the mixture is uniformly stirred after ultrasonic dispersion, and the mixture is heated in a reaction kettle at 180 ℃ for 8 hours. The obtained composite material is washed by deionized water and ethanol for 3 times and dried for 12 hours at 80 ℃. Preparing the Bi/BiOCOOH nano composite material.
Synthesis of Bi/BiOCOOH/PVDF
0.3g PVP (polyvinylpyrrolidone) powder was dissolved in 7.89mL DMF (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring; 0.1g of the catalyst Bi/BiOCOOH is ground and put into the solution, and the mixture is stirred uniformly, so that the mass percentage of the catalyst in the solution is 1%.
2.1g of PVDF (polyvinyl fluoride) powder are dissolved in the above solution and mechanically stirred at 50 ℃ for 12h to form a solution; degassing the solution at constant temperature for 12h to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, immersing the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until use. After the film material is completely formed, the filter paper is used for absorbing and removing redundant water and is placed in the freshness protection package for subsequent use.
By the method, the Bi-based photocatalytic material loaded by the PVDF film is prepared, and is 1% Bi/BiOCOOH/PVDF.
Example 2
Step 1, synthesis of BiOCOOH by solvothermal method
Adding Bi (NO) 3 ) 3 ·5H 2 O (4 mmol) (1.94 g) was dissolved in 20mL DMF and 10mL water with vigorous stirring. After dissolution, 50mL of glycerol (glycerin) was added to the above solution, and stirred uniformly so that the solution became clear after dissolution of each substance. The obtained solution was poured into an autoclave having a volume of 100mL, and after solvothermal reaction at 160 ℃ for 24h, the initial product of BiOCOOH was produced. After the reaction is finished, washing the collected product for 3 times by using deionized water and ethanol, finally transferring the product into an oven, and drying the product for 15 hours at 60 ℃ to obtain BiOCOOH powder;
step 2. Synthesis of Bi/BiOCOOH
The Bi/BiOCOOH nano composite material is prepared by adopting a simple solvothermal method, and the specific process comprises the following steps:
0.021g Bi(NO 3 ) 3 ·5H 2 o was dissolved ultrasonically in 65mL Ethylene Glycol (EG). 0.42g of BiOCOOH powder was then added to the above solution, in which Bi (NO) was present 3 ) 3 ·5H 2 The mass fraction of O in the BiOCOOH powder is 5 percent, the mixture is stirred evenly after ultrasonic dispersion,heating the mixture in a reaction kettle at 180 ℃ for 8h. The obtained composite material is washed by deionized water and ethanol for 3 times and dried for 12 hours at 80 ℃. Preparing the Bi/BiOCOOH nano composite material.
Synthesis of Bi/BiOCOOH/PVDF
Dissolving 0.3g of PVP (polyvinylpyrrolidone) powder in 7.68mL of DMF (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring; 0.3g of the catalyst Bi/BiOCOOH is ground and put into the solution, and the mixture is stirred uniformly, so that the mass fraction of the catalyst in the solvent is 3 percent.
2.1g of PVDF (polyvinyl fluoride) powder are dissolved in the above solution and mechanically stirred at 50 ℃ for 12 hours to form a solution; degassing the solution for 12h at constant temperature to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, soaking the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until the formed film is used. After the film material is completely formed, the filter paper is used for absorbing and removing redundant water and is placed in the freshness protection package for subsequent use.
By the method, the Bi-based photocatalytic material loaded by the PVDF film is prepared, and is 3% Bi/BiOCOOH/PVDF.
Example 3
Step 1. Synthesis of BiOCOOH by Solvothermal Process
Adding Bi (NO) 3 ) 3 ·5H 2 O (4 mmol) (1.94 g) was dissolved in 20mL DMF and 10mL water with vigorous stirring. After dissolution, 50mL of glycerol (glycerin) was added to the above solution, and stirred uniformly so that the solution became clear after dissolution of each substance. The obtained solution was poured into an autoclave having a volume of 100mL, and after solvothermal reaction at 160 ℃ for 24h, the initial product of BiOCOOH was produced. After the reaction is finished, washing the collected product for 3 times by using deionized water and ethanol, finally transferring the product into an oven, and drying the product for 15 hours at 60 ℃ to obtain BiOCOOH powder;
step 2. Synthesis of Bi/BiOCOOH
The Bi/BiOCOOH nano composite material is prepared by adopting a simple solvothermal method, and the specific process comprises the following steps:
0.021g Bi(NO 3 ) 3 ·5H 2 o was dissolved ultrasonically in 65mL Ethylene Glycol (EG). 0.42g of BiOCOOH powder is then added to the above solution, in which Bi (NO) is present 3 ) 3 ·5H 2 And O accounts for 5% of the BiOCOOH powder by mass, is uniformly stirred after being dispersed by ultrasonic waves, and is heated for 8 hours at 180 ℃ in a reaction kettle. The obtained composite material is washed 3 times by deionized water and ethanol and dried for 12h at 80 ℃. Preparing the Bi/BiOCOOH nano composite material. BiOCOOH in the composite material is composed of 3D flower-like microspheres with uniform size (FIG. 3A-B). 5% Bi/BiOCOOH surface had both a uniform flower-like microsphere structure and a somewhat lamellar structure, which was probably formed by BiOCOOH after the second hydrothermal treatment which had destroyed the original part of the flower-like microspheres.
Synthesis of Bi/BiOCOOH/PVDF
Dissolving 0.3g of PVP (polyvinylpyrrolidone) powder in a 7.47ml dmdff (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring; grinding 0.5g of catalyst Bi/BiOCOOH, putting into the solution, and uniformly stirring;
2.1g of PVDF (polyvinyl fluoride) powder is dissolved in the solution and mechanically stirred for 8-15 hours at 50 ℃ to form a solution; degassing the solution for 12h at constant temperature to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, soaking the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until the formed film is used. After the film material is completely formed, the filter paper is used for absorbing and removing redundant water and is placed in the freshness protection package for subsequent use.
By the method, the Bi-based photocatalytic material loaded by the PVDF film is prepared, and is 5% Bi/BiOCOOH/PVDF.
Example 4
Step 1, biOCOOH synthesis is carried out by solvothermal method
Adding Bi (NO) 3 ) 3 ·5H 2 O (4 mmol) (1.94 g) was dissolved in 20mL DMF and 10mL water with vigorous stirring. After dissolution, 50mL of glycerol (glycerin) was added to the above solution, and the mixture was stirred well to dissolve the substances, so that the solution became clearAnd (5) clearing. The obtained solution was poured into an autoclave having a volume of 100mL, and after solvothermal reaction at 160 ℃ for 24 hours, an initial product of BiOCOOH was produced. After the reaction is finished, washing the collected product for 3 times by using deionized water and ethanol, finally transferring the product into an oven, and drying the product for 15 hours at 60 ℃ to obtain BiOCOOH powder;
step 2. Synthesis of Bi/BiOCOOH
The Bi/BiOCOOH nano composite material is prepared by adopting a simple solvothermal method, and the specific process comprises the following steps:
0.021g Bi(NO 3 ) 3 ·5H 2 o was dissolved ultrasonically in 65mL Ethylene Glycol (EG). 0.42g of BiOCOOH powder is then added to the above solution, in which Bi (NO) is present 3 ) 3 ·5H 2 The mass ratio of O in the BiOCOOH powder is 1-7%, the mixture is uniformly stirred after ultrasonic dispersion, and the mixture is heated in a reaction kettle for 8 hours at 180 ℃. The obtained composite material is washed 3 times by deionized water and ethanol and dried for 12h at 80 ℃. Preparing the Bi/BiOCOOH nano composite material. BiOCOOH in the composite material is composed of 3D flower-shaped microspheres with uniform size (figures 3A-B). 5% Bi/BiOCOOH surface has both a uniform flower-like microspherical structure and some sheet-like structures which may be formed by BiOCOOH after the second hydrothermal treatment by destroying the original part of flower-like microspherical structure.
Synthesis of Bi/BiOCOOH/PVDF
Dissolving PVP (polyvinylpyrrolidone) powder in a DMF (N, N-dimethylformamide) (ρ = 0.950) solvent under mechanical stirring; grinding 0.7g of Bi/BiOCOOH, putting into the solution, and uniformly stirring;
PVDF (polyvinyl fluoride) powder is dissolved in the solution and is mechanically stirred for 8 to 15 hours at the temperature of 40 to 80 ℃ and 50 ℃ for 12h to form solution; degassing the solution for 12h at constant temperature to eliminate bubbles, scraping the solution on a glass plate by using a film scraper, soaking the formed film in deionized water, cleaning the formed film with the deionized water every 6h on the first day to remove residual solvent, and storing the formed film in the deionized water until the formed film is used. After the film material is completely formed, the filter paper is used for absorbing and removing redundant water and is placed in the freshness protection package for subsequent use.
By the method, the Bi-based photocatalytic material loaded by the PVDF film is prepared, and is Bi/BiOCOOH/PVDF with the concentration of 7%.
BiOCOOH and 5% Bi/BiOCOOH were observed by scanning electron microscopy (FIG. 1). As is clear from FIG. 1, biOCOOH is composed of 3D flower-like microspheres (A-B in FIG. 1) of uniform size. 5% Bi/BiOCOOH surface has both a uniform flower-like microspherical structure and some sheet-like structures which may be formed by BiOCOOH after the second hydrothermal treatment by destroying the original part of flower-like microspherical structure. Comparison of BiOCOOH (FIG. 3A) with 5% Bi/BiOCOOH (FIG. 3B) revealed that, 5% Bi/BiOCOOH, on flower-like microspheres, had some particulate matter accumulated, most likely the formation of elemental bismuth. It can be demonstrated from the re-transmission plots, furthermore, the EDS maps (FIGS. 3C-F) show the Bi, C and O elements in the 5% Bi/BiOCOOH nanoparticles.
The top appearance of the membrane catalyst can be seen from fig. 2 (a, B, C, D, E), as the catalyst increases, the pores on the membrane surface become less and less, and fragments and wrinkles appear on the surface, because the catalyst increases and some of the catalyst are stacked together to form microscopic flakes, and when the membrane catalyst is in static degassing, part of the catalyst may precipitate downwards, and the catalyst content of the solutions with different heights is different, so that cracks and wrinkles appear on the membrane surface during the membrane scraping process. Cross-section of the membrane catalyst as can be seen in fig. 2 (F, G, H, I, J), the uppermost layer is a thin and dense layer which contributes to the activity and selectivity of the membrane, the bottom layer is finger-shaped, has larger pores, supports the membrane surface layer, and facilitates the transmission of light. With the increase of the catalyst, the pores of the membrane are hardly changed, and the original structural characteristics of the membrane are maintained.
5% the elemental composition and binding energy of Bi/BiOCOOH/PVDF can be demonstrated by XPS plots (FIGS. 3A-D). XPS survey showed the coexistence of Bi, O and C elements, consistent with the sample composition of the photocatalyst. The high resolution C1s XPS spectrum (fig. 3B) shows that the peak at 284.3eV may be related to an adventitious carbon, while the peaks at 285.7eV and 290.2eV belong to carbons in the carboxyl group. In the O1s XPS spectrum (FIG. 3C), the two peaks located at 529.8eV and 531.6eV belong to the oxygen in the Bi-O bond and-COOH, respectively. The high resolution Bi 4f XPS spectra (FIG. 3D) show two at 158.5eV and 163.7eVPeaks are of Bi 4f 7/2 And Bi 4f 5/2 While the two peaks at 157.4eV and 162.6eV belong to the semimetallic bismuth. These results are consistent with the XRD characterization and also indicate 5% of the simultaneous presence of BiOCOOH and Bi in Bi/BiOCOOH/PVDF.
From XRD (FIG. 3E), the crystallinity and crystal phase of the four materials BiOCOOH,5% Bi/BiOCOOH, PVDF, 5% Bi/BiOCOOH/PVDF, respectively, can be seen. The diffraction peak position of BiOCOOH is matched with standard card (JCPDS No. 35-0939) of BiOCOOH, wherein 24.33 degrees, 28.82 degrees, 32.52 degrees, 35.06 degrees, 41.86 degrees, 46.53 degrees, 53.44 degrees and 55.69 degrees respectively correspond to crystal planes (101), (102), (110), (103), (113), (200), (211) and (212), and the material is proved to be successfully prepared. 5% Bi/BiOCOOH, the diffraction peak positions corresponding to the diffraction peaks of the (012), (104) and (110) crystal planes at 24.33 °, 37.9 ° and 39.62 °, respectively, coincided with those of standard card of elemental Bi (JCPDS No. 85-1329), in addition to the coincidence with BiOCOOH. The (110) crystal plane at 20.16 ° is the characteristic diffraction peak of PVDF. 5% the diffraction peaks of Bi/BiOCOOH/PVDF were also almost coincident with the characteristic diffraction peaks of the standard cards (JCPDS No. 35-0939), (JCPDS No. 85-1329) and PVDF. This also demonstrates the successful preparation of the composite.
BiOCOOH,5% Bi/BiOCOOH and 5% N of Bi/BiOCOOH/PVDF as shown in FIG. 3F 2 The absorption-desorption type IV isotherms all show a type IV curve of H3 hysteresis loop, indicating the presence of mesopores (2-50 nm), possibly due to narrow slit-like pores formed by flower-like microsphere morphology. In addition, the corresponding pore size distribution curve (fig. 3G) indicates that most of the pores are distributed from 2 to 30nm, which is consistent with the results of nitrogen adsorption-desorption isotherms, confirming the presence of mesopores. The sharp peak of about 2.5nm for all samples is probably due to the narrow slit-like pores formed by the morphology of the BiOCOOH flower-like microspheres and the presence of voids between the nanoparticles (observed in the SEM images). According to related reports, the mesoporous structure of the catalyst can provide an effective transport path for photo-generated carriers and reactants, and is beneficial to improving the photocatalytic activity.
BiOCOOH,5%Bi/BiOCOOH and 5%the light absorption characteristics of Bi/BiOCOOH/PVDF are revealed by ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) (FIG. 4A). Pure BiOCOOH has a very low light absorption intensity in the visible wavelength range. 5% Bi/BiOCOOH and 5% Bi/BiOCOOH/PVDF as effective as possible in enhancing the light-absorbable intensity and shifting the maximum absorption peak position toward the red wave direction, which can be attributed to the elementary Bi surface plasmon resonance effect, which contributes to the improvement of the optical properties of BiOCOOH and contributes to the improvement of the utilization of light in the photocatalytic reaction. In addition, the corresponding band gap energy (Eg) value is calculated by using a Tauc/David-Mott model, and the formula is as follows:
αhv＝A(hv-E g ) n2
wherein alpha, h, nu, A and Eg are absorption coefficient, planck constant, vibration frequency, proportionality constant and band gap energy respectively. BiOCOOH,5% Bi/BiOCOOH and 5% Bi/BiOCOOH/PVDF were calculated to have band gap energies of 2.9eV, 3.2eV and 3.34eV, respectively.
The corresponding valence band energy level analysis was measured using XPS valence band spectroscopy (figure 4C). 5% Bi/BiOCOOH/PVDF had a VB of 1.38eV. Furthermore, the CB value of 5% Bi/BiOCOOH/PVDF can be calculated by the following formula:
E g ＝E VB -E CB
wherein E CB And E VB CB and VB, eg, which are semiconductors, respectively, are the band gaps of the material. Calculated as 5% CB of Bi/BiOCOOH/PVDF of-1.82 eV.
The recombination rate of the photo-generated electron-hole pairs was investigated. BiOCOOH,5% Bi/BiOCOOH and 5% Bi/BiOCOOH/PVDF Photoluminescence (PL) spectra, see FIG. 4D.5% Bi/BiOCOOH and 5% Bi/BiOCOOH/PVDF has a PL intensity lower than that of BiOCOOH, which means a low rate of recombination of photogenerated carriers, improving the defect that BiOCOOH photogenerated carriers are easily recombined.
Carrier separation and transfer efficiency are key factors affecting photocatalytic efficiency. As can be seen from FIG. 4E, 5% Bi/BiOCOOH had a high current density, indicating that it had better carrier separation efficiency. At the same time, fig. 4F can obtain, 5%/BiOCOOH having the smallest radius of the arc, which also demonstrates the excellent photogenerated carrier characteristics, which is consistent with the results of fig. 4E, demonstrating the excellent photocatalytic activity of elementary Bi-modified BiOCOOH.
As can be seen from FIG. 5A, 5% of the catalytic efficiency of Bi/BiOCOOHThe best result is obtained. As can be seen from FIG. 5B, 5% of Bi/BiOCOOH/PVDF has the optimum photocatalytic effect. Comparing the three different catalysts, FIG. 5C shows that 5% Bi/BiOCOOH/PVDF photocatalyst, which supported the polymer film, had almost the same degrading effect on ciprofloxacin as 5% Bi/BiOCOOH photocatalyst, which can indicate that the polymer film had almost no negative effect on the photocatalytic degradation, i.e., that the polymer film-supported photocatalyst had excellent photocatalytic performance. As can be seen from FIGS. 5D and E, SO 4 2- And a pH of 7 with minimal effect on photocatalytic degradation.
In order to explore a possible mechanism of degrading ciprofloxacin by photocatalysis, a free radical detection experiment analyzes free radicals which play a main role in the degradation process of ciprofloxacin tablets. From FIGS. 6A and B, it can be found that the active species that plays a major role in the photocatalytic degradation process is O 2- And OH. The structural and stable performance of the catalyst is also important in photocatalytic degradation processes. Under the same test conditions, the Bi/BiOCOOH/PVDF photocatalytic material was subjected to 4-cycle photocatalytic performance tests (as shown in fig. 6C). With the increase of the use times, the photocatalytic degradation capability of the photocatalytic material is slightly reduced, the first degradation efficiency is 89%, and the degradation efficiency after 4 cycles is 87%, which shows that the catalyst loaded by the polymer film is almost unchanged in the photocatalytic degradation process (as shown in a graph D), and after the catalyst is recycled for 4 times, the catalyst still has high degradation efficiency on the photocatalytic degradation of ciprofloxacin, and shows that the composite material has good stability.
A possible photocatalytic mechanism is proposed based on the above studies as shown in fig. 7. BiOCOOH emits electrons when irradiated by external light greater than its Eg, and the separated electrons migrate to the conduction band, while the valence band leaves holes equal in number to the electrons. Electrons in the BiOCOOH conduction band can be rapidly transferred into the elementary substance Bi, so that the separation of electron-hole pairs is remarkably promoted. These separated electrons react with dissolved oxygen in the system to form O 2 - It is these active substances that the free radical and the cavity directly react with water in the system to generate OH free radical and the cavity itself oxidizes ciprofloxacinSuch that ciprofloxacin is degraded.
Example 5
In this example, bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to BiOCOOH powder was 1%, and the rest was the same as in example 1.
Example 6
In this example, bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to BiOCOOH powder was 3%, and the rest was the same as in example 1.
Example 7
Bi (NO) in this example 3 ) 3 ·5H 2 The mass ratio of O to BiOCOOH powder was 5%, and the rest was the same as in example 1.
Example 8
Bi (NO) in this example 3 ) 3 ·5H 2 The mass ratio of O to BiOCOOH powder was 7%, and the rest was the same as in example 1.
Example 9
In step 2 of this example, the reaction temperature in the reaction kettle was 150 ℃, the reaction time was 8 hours, and the remaining parameters and steps were the same as those of example 1.
Example 10
In step 2 of this example, the reaction temperature in the reaction kettle was 180 ℃, the reaction time was 8 hours, and the remaining parameters and steps were the same as those of example 1.
Example 11
In step 2 of this example, the reaction temperature in the reaction kettle was 160 ℃, the reaction time was 8 hours, and the remaining parameters and steps were the same as those of example 1.
Example 12
In the step 2 of the present example, the reaction temperature in the reaction kettle is 170 ℃, the reaction time is 8h, and the rest parameters and steps are the same as those of the example 1.
Example 13
In step 3 of this example, the mechanical stirring temperature is 40 ℃ and the mechanical stirring time is 15h.
Example 14
In step 3 of this example, the mechanical stirring temperature is 50 ℃ and the mechanical stirring time is 12h.
Example 15
In step 3 of this example, the mechanical stirring temperature is 70 ℃ and the mechanical stirring time is 10 hours.
Example 16
In step 3 of this example, the mechanical stirring temperature is 80 ℃ and the mechanical stirring time is 8h.
BiOCOOH is used as an active Ultraviolet Light Driving (ULD) photocatalyst and has the advantages of high chemical stability, low consumption, strong photooxidation-reduction driving force, strong activity and the like. However, the wide band gap of BiOCOOH (e.g =3.4 eV) severely limits its practical application, and thus it needs to be modified to improve photocatalytic performance. Modification of semiconductors forming metal-semiconductor hybrids with noble metals such as Au, ag, pt, pd, etc. has been extensively studied and used to accelerate charge separation and solar spectral absorption. In view of the high cost of these precious metals, a number of low cost and readily available metals have been developed.
However, since the small-particle composite nanomaterial is easily agglomerated, it is difficult to recover in practical applications, which affects the photocatalytic performance of the composite semiconductor material and the reusability of the photocatalyst. The hybrid photocatalytic film material has outstanding recycling performance and has the characteristics of good light transmission, good porous performance and the like, and the photocatalyst is immobilized on a porous polymer to gradually attract attention of people. Polyvinylidene fluoride (PVDF) is a common building membrane material due to its unique oxidation resistance and film forming characteristics, and is also a common electrochemical auxiliary base material. The novel porous hybrid membrane material is prepared by combining PVDF and the photocatalyst on the basis of preparing the novel photocatalyst so as to solve the problems that the photocatalyst is not easy to recover, so that the activity of the photocatalyst is reduced and the photocatalyst is partially gathered in the reaction process, so that the degradation effect on the ciprofloxacin in water is improved.
The photocatalytic film material with good photocatalytic performance and convenient reuse is prepared by a hydrothermal method (150-180 ℃, 20-30 h) and a phase conversion method (40-80 ℃, 8-15 h)
The wide bandgap of BiOCOOH (Eg =3.4 eV) severely limits its practical applications. The utilization rate of visible light is low, and the photo-generated electron-hole pairs are easy to recombine, so that the efficiency of degrading the antibiotic wastewater is poor. But semimetal bismuth as a direct plasma photocatalyst has been proved to have good photocatalytic activity, and the Surface Plasmon Resonance (SPR) effect thereof has special electronic characteristics, similar to noble metals, and can improve the defects of BiOCOOH. The recycling rate of the powdery nanometer material is low, the economical efficiency is poor, and a novel porous hybrid membrane material is prepared by combining PVDF and a photocatalyst on the basis of preparing a novel photocatalyst so as to solve the problems of photocatalyst loss caused by difficult recycling of the photocatalyst and partial gathering of the photocatalyst in the reaction process, thereby improving the degradation effect of ciprofloxacin in water.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (10)

  1. A preparation method of a Bi-based photocatalytic material loaded by a PVDF (polyvinylidene fluoride) film is characterized by comprising the following steps of:
    step 1, adding Bi (NO) 3 ) 3 ·5H 2 Dissolving O in a mixed solvent of DMF and water, adding glycerol after dissolving, stirring to obtain a clear solution A, carrying out solvothermal reaction on the clear solution A to obtain a reaction product B, washing the reaction product B, and drying to obtain BiOCOOH powder;
    step 2, adding Bi (NO) 3 ) 3 ·5H 2 Dissolving O in ethylene glycol to obtain a solution C; adding BiOCOOH powder into the solution C to obtain a reaction solution D, heating the reaction solution D for reaction, and washing a reaction product to obtain a Bi/BiOCOOH nano composite material;
    and 3, dissolving PVP in DMF to obtain a solution E, adding the Bi/BiOCOOH nano composite material into the solution E, uniformly stirring to obtain a mixed solution F, adding PVDF into the mixed solution F, stirring to form a film forming solution G, and preparing the film forming solution into a film shape to obtain the Bi-based photocatalytic material loaded by the PVDF film.
  2. 2. The method for preparing a Bi-based photocatalytic material supported on a PVDF membrane as claimed in claim 1, wherein in step 1, bi (NO) 3 ) 3 ·5H 2 The mixing ratio of O, DMF and glycerol is as follows: 4mmol:30mL of: 50mL.
  3. 3. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane as claimed in claim 1, wherein in step 1, the solvothermal reaction temperature is 160 ℃ and the solvothermal reaction time is 24h.
  4. 4. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane as claimed in claim 1, wherein, in the step 2, bi (NO) is added 3 ) 3 ·5H 2 O accounts for 2 to 6 percent of the mass of the BiOCOOH powder.
  5. 5. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane as claimed in claim 1, wherein in step 2, the reaction solution D is heated at a reaction temperature of 150-180 ℃ for 8h.
  6. 6. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane according to claim 1, wherein in step 3, the mixing ratio of PVP and DMF is 0.3g: (7.26-8) mL.
  7. 7. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane as claimed in claim 1, wherein in step 2, after the Bi/BiOCOOH nanocomposite material is added into the solution E, the stirring temperature is 40-80 ℃, and the stirring time is 8-15 h.
  8. 8. The method for preparing a Bi-based photocatalytic material supported by a PVDF membrane as claimed in claim 1, wherein the amount of Bi/BiOCOOH nanocomposite added is 1-7%.
  9. 9. A PVDF-membrane-supported Bi-based photocatalytic material produced by the production method according to any one of claims 1 to 8, comprising a PVDF membrane, wherein the PVDF membrane is supported with flower-like BiOCOOH, and the BiOCOOH is supported with Bi nanoparticles.
  10. 10. Use of the PVDF membrane supported Bi-based photocatalytic material of claim 9 for the degradation of antibiotics in water.
CN202211064362.8A 2022-08-31 2022-08-31 PVDF (polyvinylidene fluoride) membrane loaded Bi-based photocatalytic material as well as preparation method and application thereof Pending CN115430462A (en)

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