CN113198532A - LDHs (F) @ PVDF-HFP composite porous foam material and preparation method and application thereof - Google Patents

LDHs (F) @ PVDF-HFP composite porous foam material and preparation method and application thereof Download PDF

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CN113198532A
CN113198532A CN202110384467.0A CN202110384467A CN113198532A CN 113198532 A CN113198532 A CN 113198532A CN 202110384467 A CN202110384467 A CN 202110384467A CN 113198532 A CN113198532 A CN 113198532A
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pvdf
hfp
ldhs
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CN113198532B (en
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李彬榕
戴敬宜
冯永海
孟敏佳
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Jiangsu University
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    • 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
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
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Abstract

The invention belongs to the technical field of chemical material preparation, and relates to an LDHs (high density polyethylene) (F) @ PVDF-HFP composite porous foam material, and a preparation method and application thereof. The invention uses NaCl as a template to manufacture a penetrating macroporous structure to obtain the three-dimensional porous PVDF-HFP foam with adjustable pore channel size, which contains a large amount of fluorine with strong electronegativity and forms metal-fluorine coordination with metal ions, thereby providing a growth site for Layered Double Hydroxides (LDHs) of transition metals, and LDHs are uniformly loaded on the PVDF-HFP foam in an array form under the assistance of ammonium fluoride to obtain the LDHs (F) @ PVDF-HFP composite porous foam material with complex three-dimensional channels. The preparation process is simple, different shapes and sizes can be prepared according to requirements, and the filler is flexible three-dimensional flexible filler. The method can be flexibly applied to catalytic packed column degradation systems of various specifications, provides a universally applicable new method for the expanded application of a PMS catalytic system, and can realize effective degradation of the wastewater in the actual environment to a certain extent.

Description

LDHs (F) @ PVDF-HFP composite porous foam material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical material preparation, and relates to an LDHs (high density polyethylene) (F) @ PVDF-HFP composite porous foam material, and a preparation method and application thereof.
Background
With the development of industry, the problem of fresh water pollution caused by chemical substances is one of the main environmental problems facing human beings, which not only affects the stability of the biological chain of the water body, but also harms human health. Therefore, the inexpensive and effective removal of contaminants from solutions has received widespread attention. A large amount of pollutants are discharged into water bodies, and water pollution is increasingly serious, wherein the dye is one of the pollutants in the water bodies. The dye variety on the market is more than 10 ten thousand, the annual output of the dye is more than 70 ten thousand tons, wherein more than 10 percent of the dye is directly discharged into rivers and lakes during the production and use processes, so that the water environment pollution is deep from the surface to the underground. Therefore, exploring a simple, efficient and low-cost method for removing dye pollutants in water body to recover safe and reliable reclaimed water has become a hot topic in the field of environmental protection.
The catalytic oxidation method is characterized in that the catalyst is utilized to generate active oxygen free radicals (OH, SO) with strong oxidation under the action of an external field or under the condition of an external reagent4·-Etc.) capable of degrading organic pollutants into small molecules that are low or non-toxic. At present, the catalyst is combined with a base material to construct a catalytic composite material which is easy to recover, and the catalytic composite material is widely applied to the field of water treatment. The common form is to combine a semiconductor catalyst and an organic membrane material by a simple blending method to form a catalytic filtration integrated water treatment system. However, in general, some common problems are common to existing processing systems, such as: the number of catalytic active sites on the membrane material per unit volume is small, the retention time of sewage in the membrane material is short, the organic pollutants with large water volume are difficult to rapidly treat, and the treatment capacity is limited; the service life of the membrane material is low due to the leakage of the catalyst, and the membrane material is difficult to regenerate; or the dye wastewater generally contains a large amount of inorganic salt components, the catalytic degradation efficiency is reduced due to high salinity, and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a composite porous foam material of ldhs (f) @ PVDF-HFP, which is a composite porous foam material of the present invention. The foam material has high fluorine content, and LDHs is uniformly loaded on PVDF-HFP foam in an array form through metal-fluorine coordination. Can be used as a three-dimensional flexible filler to construct a catalytic packed column degradation system.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides an LDHs (F) @ PVDF-HFP composite porous foam material, wherein the foam material takes PVDF-HFP foam with adjustable pore canal size as a carrier, and LDHs are loaded on the PVDF-HFP foam in an array form.
The invention also provides a preparation method of the LDHs (F) @ PVDF-HFP composite porous foam material, which comprises the following steps:
(1) putting NaCl into a ball mill for ball milling to obtain NaCl powder; uniformly grinding PVDF-HFP powder and NaCl powder to obtain a mixture, transferring the mixture into a mold, putting the mold into an oven for heating, and taking out after natural cooling; putting the obtained product and a mould into deionized water for repeated soaking to obtain PVDF-HFP foam;
(2) mixing metal salt A, metal salt B, urea and NH4F is dissolved in deionized water together to form a mixed solution; and (2) completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking the PVDF-HFP foam in the mixed solution for a period of time, transferring the PVDF-HFP foam into a reaction kettle for reaction, and washing the product with deionized water and ethanol to obtain the LDHs (F) @ PVDF-HFP composite porous foam material.
Further, the rotating speed of the ball mill in the step (1) is 100-500 rpm, the ball milling time is 10-50 h, and the ball-material ratio is 5-20: 1.
the mass ratio of the PVDF-HFP to the NaCl powder in the step (1) is 1: 5 to 9.
The grinding time in the step (1) is at least 30 min; the heating temperature is 200 ℃, and the heating time is 30-60 min.
In the step (1), the pore diameter of the PVDF-HFP foam is 300-500 microns.
In the step (2), the metal salt A is CoCl2·6H2O、FeCl3·6H2O or CuCl2·2H2O; the metal salt B is FeCl3·6H2O、CuCl2·2H2O or NiCl2·6H2O。
In the step (2), the proportion relationship of the metal salt A, the metal salt B, the urea, the ammonium fluoride and the deionized water is 5 mmol: 1-5 mmol: 12 mmol: 4-20 mmol: 60 mL.
The soaking time in the step (2) is 30-60 min; the reaction temperature of the reaction kettle is 90 ℃, and the reaction time is 12-18 h.
The invention also provides application of the LDHs (F) @ PVDF-HFP composite porous foam material in the field of dye wastewater degradation. Can be applied to activating PMS and degrading organic dye wastewater.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses NaCl as a pore-making template to manufacture a penetrating macroporous structure, obtains three-dimensional porous PVDF-HFP foam with adjustable pore canal size after dissolving the NaCl, the PVDF-HFP foam contains a large amount of fluorine (F) with strong electronegativity, and forms metal-fluorine coordination with metal ions, thereby providing growth sites for Layered Double Hydroxides (LDHs) of transition metals, and the LDHs is uniformly loaded on the PVDF-HFP foam in an array form under the assistance of ammonium fluoride to obtain LDHs (F) @ PVDF-HFP composite porous foam material with complex three-dimensional channels.
On the other hand, the metal-F coordination bond can promote the valence change of metal ions in the catalytic process, so that the activation efficiency of the Peroxymonosulfate (PMS) is improved, the yield of free radicals is increased, and the degradation performance is improved; by changing the exposure ratio of different metal components in the LDH, the electronic configuration around the metal atoms can be adjusted, and the stability and the catalytic activity of a catalytic system are further improved. In addition, the three-dimensional channel of the LDHs (F) @ PVDF-HFP porous foam material can increase the retention time of wastewater and increase the contact with pollutants; because the chloride ions can promote the activation of PMS, the catalytic performance of the composite porous foam is promoted under the condition of high salinity, and the composite porous foam can be easily suitable for the treatment of dye wastewater with high salinity.
The LDHs (F) @ PVDF-HFP composite porous foam material disclosed by the invention is simple in preparation process, can be prepared into different shapes and sizes according to requirements, and is a flexible three-dimensional flexible filler. The method can be flexibly applied to catalytic packed column degradation systems of various specifications, provides a universally applicable new method for the expanded application of a PMS catalytic system, and can realize effective degradation of the wastewater in the actual environment to a certain extent.
Drawings
FIG. 1 is a pictorial representation of the morphology of a syntactic porous foam prepared; in the figure, a is PVDF-HFP foam; b is Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, c is Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, d is cut Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, e is Co with different shapes and sizes5Fe2.5Ldhs (f) @ PVDF-HFP composite porous foams;
FIG. 2 is a surface SEM image of a prepared composite porous foam; in the figure, a is Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, b is Co5Fe2.5Ldhs (f) @ PU composite cellular foams;
FIG. 3 is a graph comparing the degradation performance of different LDHs (F) @ PVDF-HFP composite porous foams.
Detailed Description
The present invention will be further described by the following examples, however, the scope of the present invention is not limited to the following examples. The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. The following examples are examples of experimental methods not indicating specific conditions, and the detection is usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers. The reagents used in the following examples are all commercially available.
Example 1
(1) Weighing 70g of NaCl, putting the NaCl into a ball mill, and mixing the NaCl solution at a rotating speed of 100rpm and a ball-material ratio of 5: 1, ball-milling for 10 hours to obtain micron-sized uniform NaCl powder; mixing 10g of commercially available PVDF-HFP powder and 70g of NaCl powder, fully and uniformly grinding to obtain a mixture, transferring the mixture to a plurality of columnar glass molds, putting 4-12 g of the mixture into each mold, putting the molds into an oven, heating for 30min at 200 ℃, and taking out after natural cooling; putting the mould and the mould into hot deionized water for repeated soaking until all NaCl is dissolved to obtain PVDF-HFP foam; the pore diameter of the foam is about 300-500 microns through observation and measurement of a field emission scanning electron microscope.
(2) Adding 5mmol of CoCl2·6H2O, 2.5mmol of FeCl3·6H2O, 12mmol of urea and 8.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 90 ℃ for 12h, and finally washing with deionized water and ethanol to obtain Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam.
Example 2
Adding 5mmol of CoCl2·6H2O, 2.5mmol of FeCl3·6H2Dissolving O and 12mmol of urea in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 90 ℃ for 12h, and finally washing with deionized water and ethanol to obtain Co5Fe2.5LDHs @ PVDF-HFP composite porous foams.
FIG. 1 is a morphology of a composite cellular foam material prepared; in the figure, a is the PVDF-HFP foam prepared in example 1; b is Co prepared as above5Fe2.5LDHs @ PVDF-HFP composite porous foam, c is Co prepared in example 15Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, d is cut Co5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, e is Co with different shapes and sizes5Fe2.5(LDHs (F)) @ PVDF-HFP composite porous foam entity diagram; as can be seen from FIG. 1, the prepared composite material has a macroscopic porous structure, has three-dimensional channels inside, and can be customized into different foam shapes and sizes according to different application requirements. Pure PVDF-HFP foam is white, and the foam turns yellow after being loaded with CoFeLDH; co without ammonium fluoride addition5Fe2.5The LDHs @ PVDF-HFP composite porous foam is light in color, and the LDH is flaky in appearance, so that the prepared Co is5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam is darker in color, and the LDH morphology is needle-shaped.
Example 3
Prepared in this example to haveCoFe-LDHs (F) @ PVDF-HFP composite porous foam with different metal raw material proportioning relations. The preparation method is the same as that of example 1, except that CoCl is changed under the condition of ensuring that other process conditions are not changed2·6H2O and FeCl3·6H2O, mixing CoCl2·6H2O and FeCl3·6H2Adjusting the dosage of O to be 5mmol, 5mmol and 1mmol respectively to prepare Co5Fe5LDHs (F) @ PVDF-HFP composite porous foam and Co5Fe1LDHs (F) @ PVDF-HFP composite porous foam.
Example 4
Weighing 70g of NaCl, putting the NaCl into a ball mill, and mixing the NaCl solution at a rotating speed of 200rpm and a ball-material ratio of 5: 1, ball-milling for 20 hours to obtain micron-sized uniform NaCl powder; adding 10g of PVDF-HFP powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into molds with proper sizes, putting a proper amount of the mixture into each mold, putting the mixture and the molds into an oven, heating for 30min at 200 ℃, and taking out after natural cooling; putting the product and the mould into hot deionized water for repeated soaking until all NaCl is dissolved, and finally obtaining PVDF-HFP foam;
(2) adding 5mmol of CoCl2·6H2O, 2.5mmol of NiCl2·6H2O, 12mmol of urea and 4.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking the PVDF-HFP foam in the mixed solution for 60min, transferring the PVDF-HFP foam and the mixed solution to a reaction kettle, reacting for 18h at the temperature of 80 ℃, and finally washing with deionized water and ethanol to obtain Co5Ni2.5LDHs (F) @ PVDF-HFP composite porous foam.
Example 5
Weighing 70g of NaCl, putting the NaCl into a ball mill, and mixing the NaCl solution at a rotating speed of 100rpm and a ball-material ratio of 20: 1, ball-milling for 50 hours to obtain micron-sized uniform NaCl powder; adding 10g of PVDF-HFP powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into molds with proper sizes, putting a proper amount of the mixture into each mold, putting the mixture and the molds into an oven, heating for 30min at 200 ℃, and taking out after natural cooling; putting the product and the mould into hot deionized water for repeated soaking until all NaCl is dissolved, and finally obtaining PVDF-HFP foam;
(2) adding 5mmol of CoCl2·6H2O, 2.5mmol of CuCl2·2H2O, 12mmol of urea and 20.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 100 ℃ for 10h, and finally washing with deionized water and ethanol to obtain Co5Cu2.5LDHs (F) @ PVDF-HFP composite porous foam.
Example 6
In order to examine the influence of the coordination formed by the PVDF-HFP foam surface F and metal on the catalytic performance. In this example, a F-free CoFe-LDHs (F) @ PU composite porous foam was prepared.
Adding 5mmol of CoCl2·6H2O, 2.5mmol of FeCl3·6H2Dissolving O and 12mmol of urea in 60ml of deionized water together to form a mixed solution; wetting polyurethane foam (PU) without F with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 90 deg.C for 12h, and washing with deionized water and ethanol to obtain Co5Fe2.5LDHs (F) @ PU syntactic porous foam.
Co obtained in example 1 and this example was observed by scanning electron microscope5Fe2.5LDHs (F) @ PU syntactic porous foam. FIG. 2 is a surface SEM image of a prepared composite porous foam; in the figure, a is Co prepared in example 15Fe2.5LDHs (F) @ PVDF-HFP composite porous foam, b is Co5Fe2.5Ldhs (f) @ PU composite cellular foams; as can be seen from FIG. 2, Co5Fe2.5LDHs are loaded on the surface of the foam in an array form; and Co5Fe2.5The supported morphology of the LDHs (F) is changed from a sheet array to a needle array, and the LDHs (F) is more densely supported on the surface of the material, so that more catalytic sites can be exposed. The PU foam provides growth sites due to no coordination formed by F and metal, and has less LDH grown on the surface, so that the active sites are less and the catalytic reaction is slow.
Example 8
In this example, the composite porous foams prepared in examples 1 to 5 were used to degrade methyl blue, and the degradation performance was analyzed. The specific degradation process is as follows: a20 mg/L methyl blue solution containing 1mol/LPMS is prepared, and then the simulated pollutants are degraded by flowing through a catalytic packed column filled with different composite porous foams, and 10 cycles are repeated.
FIG. 3 is a graph comparing the degradation performance of different LDHs (F) @ PVDF-HFP composite porous foams; as can be seen from FIG. 3, the constructed LDHs (F) @ PVDF-HFP composite porous foam has excellent degradation effect on methyl blue, can reach more than 99% in 3min at most, and can still maintain good catalytic performance after 10 cycles. Wherein prepared Co5Fe2.5LDHs (F) @ PVDF-HFP has the optimal degradation performance, and can almost completely decolor methyl blue.
Example 9
Weighing 90g of NaCl, putting the weighed materials into a ball mill, and mixing the materials at a rotating speed of 500rpm and a ball-to-material ratio of 5: 1, ball-milling for 10 hours to obtain micron-sized uniform NaCl powder; adding 10g of PVDF-HFP powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into molds with proper sizes, putting a proper amount of the mixture into each mold, putting the mixture and the molds into an oven, heating for 60min at 200 ℃, and taking out after natural cooling; putting the product and the mould into hot deionized water for repeated soaking until all NaCl is dissolved, and finally obtaining PVDF-HFP foam;
(2) adding 5mmol of CuCl2·2H2O, 2.5mmol of NiCl2·6H2O, 12mmol of urea and 10.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 100 ℃ for 10h, and finally washing with deionized water and ethanol to obtain Cu5Ni2.5LDHs (F) @ PVDF-HFP composite porous foam.
Example 10
Weighing 70g of NaCl, putting the NaCl into a ball mill, and mixing the NaCl solution at a rotating speed of 100rpm and a ball-material ratio of 20: 1, ball-milling for 50 hours to obtain micron-sized uniform NaCl powder; adding 10g of PVDF-HFP powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into molds with proper sizes, putting a proper amount of the mixture into each mold, putting the mixture and the molds into an oven, heating for 30min at 200 ℃, and taking out after natural cooling; putting the product and the mould into hot deionized water for repeated soaking until all NaCl is dissolved, and finally obtaining PVDF-HFP foam;
(2) adding 5mmol of CuCl2·2H2O, 2.5mmol of FeCl3·6H2O, 12mmol of urea and 20.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 100 ℃ for 10h, and finally washing with deionized water and ethanol to obtain Cu5Fe2.5LDHs (F) @ PVDF-HFP composite porous foam.
Example 11
Weighing 50g of NaCl, putting the NaCl into a ball mill, and mixing the NaCl solution at a rotating speed of 500rpm and a ball-material ratio of 5: 1, ball-milling for 10 hours to obtain micron-sized uniform NaCl powder; adding 10g of PVDF-HFP powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into molds with proper sizes, putting a proper amount of the mixture into each mold, putting the mixture and the molds into an oven, heating for 30min at 200 ℃, and taking out after natural cooling; putting the product and the mould into hot deionized water for repeated soaking until all NaCl is dissolved, and finally obtaining PVDF-HFP foam;
(2) adding 5mmol of FeCl3·6H2O, 2.5mmol of NiCl2·6H2O, 12mmol of urea and 18.0mmol of NH4F are dissolved in 60ml of deionized water together to form a mixed solution; completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking in the mixed solution for 30min, transferring to a reaction kettle, reacting at 100 ℃ for 10h, and finally washing with deionized water and ethanol to obtain Fe5Ni2.5LDHs (F) @ PVDF-HFP composite porous foam.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (10)

1. The LDHs (F) @ PVDF-HFP composite porous foam material is characterized in that the foam material takes PVDF-HFP foam with adjustable pore channel size as a carrier, and LDHs are loaded on the PVDF-HFP foam in an array form.
2. A preparation method of LDHs (F) @ PVDF-HFP composite porous foam material is characterized by comprising the following steps:
(1) putting NaCl into a ball mill for ball milling to obtain NaCl powder; uniformly grinding PVDF-HFP powder and NaCl powder to obtain a mixture, transferring the mixture into a mold, putting the mold into an oven for heating, and taking out after natural cooling; putting the obtained product and a mould into deionized water for repeated soaking to obtain PVDF-HFP foam;
(2) mixing metal salt A, metal salt B, urea and NH4F is dissolved in deionized water together to form a mixed solution; and (2) completely wetting the PVDF-HFP foam obtained in the step (1) with ethanol, soaking the PVDF-HFP foam in the mixed solution for a period of time, transferring the PVDF-HFP foam into a reaction kettle for reaction, and washing the product with deionized water and ethanol to obtain the LDHs (F) @ PVDF-HFP composite porous foam material.
3. The preparation method according to claim 2, wherein the rotation speed of the ball mill in the step (1) is 100-500 rpm, the ball milling time is 10-50 h, and the ball-to-material ratio is 5-20: 1.
4. the production method according to claim 2, wherein the mass ratio of PVDF-HFP and NaCl powder in step (1) is 1: 5 to 9.
5. The method according to claim 2, wherein the time for the grinding in step (1) is at least 30 min; the heating temperature is 200 ℃, and the heating time is 30-60 min.
6. The method according to claim 2, wherein the pore size of the PVDF-HFP foam in the step (1) is 300 to 500 μm.
7. The method according to claim 2, wherein in the step (2), the metal salt A is CoCl2·6H2O、FeCl3·6H2O or CuCl2·2H2O; the metal salt B is FeCl3·6H2O、CuCl2·2H2O or NiCl2·6H2O。
8. The preparation method according to claim 2, wherein the ratio of the metal salt A, the metal salt B, the urea, the ammonium fluoride and the deionized water is 5 mmol: 1-5 mmol: 12 mmol: 4-20 mmol: 60 mL.
9. The preparation method according to claim 2, wherein the soaking time in the step (2) is 30-60 min; the reaction temperature of the reaction kettle is 90 ℃, and the reaction time is 12-18 h.
10. The use of the ldhs (f) @ PVDF-HFP composite porous foam material of claim 1 in the field of dye wastewater degradation.
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