CN113198532B - 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 PDFInfo
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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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- 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
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- 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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- 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
- 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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- 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
- 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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- 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
- 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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- 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
- 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
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- 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
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- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention belongs to the technical field of chemical material preparation, and relates to an LDHs (F) @ PVDF-HFP composite porous foam material, and a preparation method and application thereof. According to the invention, naCl is used as a template to manufacture a penetrating macroporous structure, so that a three-dimensional porous PVDF-HFP foam with adjustable pore channel size is obtained, and the porous PVDF-HFP foam contains a large amount of fluorine with strong electronegativity, and forms a metal-fluorine coordination effect with metal ions, so that growth sites are provided for Layered Double Hydroxides (LDHs) of transition metals, and the LDHs are uniformly loaded on the PVDF-HFP foam in an array form under the assistance of ammonium fluoride, so that an LDHs (F) @ PVDF-HFP composite porous foam material with complex three-dimensional channels is obtained. The preparation process is simple, and the filler can be prepared into different shapes and sizes according to the needs, so that the filler is a flexible three-dimensional flexible filler. The method can be flexibly applied to catalytic packed column degradation systems of various specifications, provides a new method which is universally applicable for the expansion application of the PMS catalytic system, and can realize the effective degradation of the wastewater in the actual environment to a certain extent.
Description
Technical Field
The invention belongs to the technical field of chemical material preparation, and relates to an LDHs (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, and not only affects the stability of biological chains of water bodies, but also endangers human health. Therefore, the inexpensive and efficient removal of contaminants from solutions has received widespread attention. A large amount of pollutants are discharged into a water body, and water pollution is more and more serious, wherein dye is one of the pollutants in the water body. The dye types in the market are more than 10 ten thousand, the annual yield 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 in the production and use processes, so that the water environment pollution goes deep into the ground from the earth surface. Therefore, a simple, efficient and low-cost method for removing dye pollutants in water body is explored, and the recovery of safe and reliable reclaimed water becomes a hot spot subject in the field of environmental protection.
The catalytic oxidation method is characterized by that under the condition of external field action or external reagent the catalyst can be used to produce active oxygen free radical (OH, SO) with strong oxidation action 4 · - Etc.) are capable of degrading organic contaminants into low-toxic or non-toxic small molecules. At present, the catalyst is combined with a substrate to construct a catalytic composite material which is easy to recycle, and the catalytic composite material has been widely applied to the field of water treatment. Among them, the common form is to combine the semiconductor catalyst and the organic film material by a simple blending method to form a catalytic filtration integrated water treatment system. However, in general, existing processing systems commonly suffer from a number of common problems, such as: the unit volume of the membrane material has fewer catalytic active sites, the residence time of the 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; catalyst leakage results in a lower lifetime of the membrane material, which is difficult to regenerate; or dye wastewater generally contains a large amount of inorganic salt components, and the salinity is high, so that the catalytic degradation efficiency is reduced, and the like.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide an LDHs (F) @ PVDF-HFP composite porous foam material, which solves the problems of the prior art. The foam material has high fluorine content, and LDHs are uniformly loaded on PVDF-HFP foam in an array form through metal-fluorine coordination. The catalyst packed column degradation system can be constructed as a three-dimensional flexible filler.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides an LDHs (F) @ PVDF-HFP composite porous foam material, which takes PVDF-HFP foam with adjustable pore canal size as a carrier, and the 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 specifically 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 the mold after natural cooling; repeatedly soaking the material and the mould in deionized water to obtain PVDF-HFP foam;
(2) Metal salt A, metal salt B, urea and NH 4 F, jointly dissolving in deionized water to form a mixed solution; and (3) soaking the PVDF-HFP foam obtained in the step (1) in the mixed solution after being completely wetted by ethanol for a period of time, transferring the mixed solution into a reaction kettle for reaction, and flushing the product by deionized water and ethanol to obtain the LDHs (F) @ PVDF-HFP composite porous foam material.
Further, in the step (1), the rotating speed of the ball mill 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 PVDF-HFP to NaCl powder in the step (1) is 1: 5-9.
The milling in step (1) takes at least 30 minutes; the heating temperature is 200deg.C, and the heating time is 30-60min.
And (3) the pore size of the PVDF-HFP foam in the step (1) is 300-500 microns.
In the step (2), the metal salt A is CoCl 2 ·6H 2 O、FeCl 3 ·6H 2 O or CuCl 2 ·2H 2 O; the metal salt B is FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O or NiCl 2 ·6H 2 O。
In the step (2), the proportion relation of the metal salt A, the metal salt B, urea, ammonium fluoride and deionized water is 5mmol: 1-5 mmol:12mmol: 4-20 mmol:60mL.
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:
according to the invention, naCl is used as a pore-forming template to manufacture a penetrating macroporous structure, after NaCl is dissolved, a three-dimensional porous PVDF-HFP foam with adjustable pore channel size is obtained, and the PVDF-HFP foam contains a large amount of fluorine (F) with strong electronegativity and forms a metal-fluorine coordination effect with metal ions, so that a growth site is provided for Layered Double Hydroxides (LDHs) of transition metals, and the LDHs are uniformly loaded on the PVDF-HFP foam in an array form under the assistance of ammonium fluoride, so that an LDHs (F) @ PVDF-HFP composite porous foam material with complex three-dimensional channels is obtained.
On the other hand, the metal-F coordination bond can promote the valence state 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, so that the stability and the catalytic activity of the catalytic system are improved. In addition, the three-dimensional channel of the LDHs (F) @ PVDF-HFP porous foam material can increase the residence time of wastewater and increase the contact with pollutants; because 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 applied to the treatment of high salinity dye wastewater.
The LDHs (F) @ PVDF-HFP composite porous foam material provided 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 new method which is universally applicable for the expansion application of the PMS catalytic system, and can realize the effective degradation of the wastewater in the actual environment to a certain extent.
Drawings
FIG. 1 is a physical form diagram of a composite porous foam material prepared; in the figure, a is PVDF-HFP foam; b is Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, c is Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, d is cut Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, e is Co with different shape and size 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam;
FIG. 2 is a surface SEM image of the prepared composite porous foam; in the figure, a is Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, b is Co 5 Fe 2.5 LDHs (F) @ PU composite porous foam;
FIG. 3 is a graph comparing degradation properties of various 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 generally and/or specifically describes the materials used in the test as well as the test methods. The experimental procedure, in which no specific conditions are noted in the examples below, is generally carried out according to conventional conditions or according to the conditions recommended by the manufacturer. The reagents used in the following examples were all commercially available.
Example 1
(1) 70g of NaCl was weighed and put into a ball mill, and the ball-to-material ratio was 5 at a rotation speed of 100 rpm: 1 ball milling for 10 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; mixing 10g of commercially available PVDF-HFP powder and 70g of NaCl powder, fully and uniformly grinding to obtain a mixture, transferring the mixture into 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 the molds after natural cooling; repeatedly soaking the mixture and the mould in hot deionized water until NaCl is completely dissolved to obtain PVDF-HFP foam; the pore size of the foam is about 300-500 microns as measured by field emission scanning electron microscopy.
(2) 5mmolCoCl 2 ·6H 2 O, 2.5mmol FeCl 3 ·6H 2 O, 12mmol of urea and 8.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 12h at 90 ℃, and finally washing the PVDF-HFP foam with deionized water and ethanol to obtain Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
Example 2
5mmolCoCl 2 ·6H 2 O, 2.5mmol FeCl 3 ·6H 2 O and 12mmol of urea are dissolved in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 12h at 90 ℃, and finally washing the PVDF-HFP foam with deionized water and ethanol to obtain Co 5 Fe 2.5 ldhs@pvdf-HFP composite porous foam.
FIG. 1 is a morphology of a composite porous foam material prepared; in the figure, a is the PVDF-HFP foam prepared in example 1; b is Co prepared as described above 5 Fe 2.5 LDHs@PVDF-HFP composite porous foam, c is Co prepared in example 1 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, d is cut Co 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, e is Co with different shape and size 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam material object diagram; as can be seen from fig. 1, the prepared composite material has a macroscopic porous structure, and a three-dimensional channel is arranged in the composite material, so that different foam shape and sizes can be customized according to different application requirements. Pure PVDF-HFP foam was white and after loading with cofldh, the foam turned yellow; co without ammonium fluoride 5 Fe 2.5 LDHs@PVDF-HFP composite porous foam is lighter in color, and is flaky in LDH morphology, so that Co is prepared 5 Fe 2.5 The LDHs (F) @ PVDF-HFP composite porous foam has a darker color, and the LDH morphology of the LDHs is needle-shaped.
Example 3
CoFe-LDHs (F) @ PVDF-HFP composite porous foam with different metal raw material proportioning relations is prepared in the embodiment. The preparation method is the same as in example 1, except that the CoCl is changed while other process conditions are kept unchanged 2 ·6H 2 O and FeCl 3 ·6H 2 Raw material ratio of O, coCl 2 ·6H 2 O and FeCl 3 ·6H 2 The dosage of O is respectively adjusted to 5mmol, 5mmol and 5mmol, 1mmol, and Co is prepared 5 Fe 5 LDHs (F) @ PVDF-HFP composite porous foam and Co 5 Fe 1 LDHs (F) @ PVDF-HFP composite porous foam.
Example 4
70g of NaCl was weighed and put into a ball mill, and the ball-to-material ratio was 5 at a rotation speed of 200 rpm: ball milling for 20 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; adding 10g PVDF-HFP powder, fully grinding uniformly to obtain a mixture, transferring the mixture into a mould with proper size, putting a proper amount of the mixture into each mould, putting the mixture together with the mould into an oven, heating for 30min at 200 ℃, and taking out the mixture after natural cooling; the product and the mould are put into hot deionized water for repeated soaking until NaCl is completely dissolved, and finally PVDF-HFP foam is obtained;
(2) 5mmolCoCl 2 ·6H 2 O, 2.5mmol NiCl 2 ·6H 2 O, 12mmol of urea and 4.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 60min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 18h at 80 ℃, and finally washing the PVDF-HFP foam with deionized water and ethanol to obtain Co 5 Ni 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
Example 5
70g of NaCl was weighed and put into a ball mill, and the ball-to-material ratio was 20 at a rotation speed of 100 rpm: 1, ball milling for 50 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; adding 10g PVDF-HFP powder, fully grinding uniformly to obtain a mixture, transferring the mixture into a mould with proper size, putting a proper amount of the mixture into each mould, putting the mixture together with the mould into an oven, heating for 30min at 200 ℃, and taking out the mixture after natural cooling; the product and the mould are put into hot deionized water for repeated soaking until NaCl is completely dissolved, and finally PVDF-HFP foam is obtained;
(2) 5mmolCoCl 2 ·6H 2 O, 2.5mmol CuCl 2 ·2H 2 O, 12mmol of urea and 20.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 10h at 100 ℃, and finally flushing the PVDF-HFP foam with deionized water and ethanol to obtain Co 5 Cu 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
Example 6
To examine the effect of the coordination of PVDF-HFP foam surface F with metal formation on catalytic performance. In this example, a CoFe-LDHs (F) @ PU composite porous foam containing no F was prepared.
5mmolCoCl 2 ·6H 2 O, 2.5mmol FeCl 3 ·6H 2 O and 12mmol of urea are dissolved 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 90deg.C for 12 hr, and washing with deionized water and ethanol to obtain Co 5 Fe 2.5 LDHs (F) @ PU composite porous foam.
Co obtained in example 1 and this example was observed by scanning electron microscopy 5 Fe 2.5 LDHs (F) @ PU composite porous foam. FIG. 2 is a surface SEM image of the prepared composite porous foam; in the figure, a is Co prepared in example 1 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam, b is Co 5 Fe 2.5 LDHs (F) @ PU composite porous foam; as can be seen from FIG. 2, co 5 Fe 2.5 LDHs are supported on the surface of the foam in an array form; and Co 5 Fe 2.5 The LDHs (F) loaded form is changed from a flaky array to a needle-shaped array, so that the LDHs (F) is more densely loaded on the surface of the material, and more catalytic sites can be exposed. PU foam has no F and metal shapeThe coordination provides growth sites, less LDH grows on the surface, resulting in fewer active sites and slow catalytic reactions.
Example 8
In this example, the composite porous foams prepared in examples 1 to 5 were used to degrade methyl blue, and degradation performance was analyzed. The specific degradation process is as follows: a solution of 20mg/L methyl blue containing 1mol/LPMS was prepared and the simulated contaminant was then passed through a catalytic packed column packed with different composite porous foams for degradation, repeating 10 cycles.
FIG. 3 is a graph comparing degradation properties of various 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, and can still maintain good catalytic performance after 10 cycles. Wherein Co is prepared 5 Fe 2.5 The LDHs (F) @ PVDF-HFP has optimal degradation performance, and almost completely decolorizes the methyl blue.
Example 9
90g of NaCl is weighed and put into a ball mill, and the ball-material ratio is 5 at the rotating speed of 500 rpm: 1 ball milling for 10 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; adding 10g PVDF-HFP powder, fully grinding uniformly to obtain a mixture, transferring the mixture into a mould with proper size, putting a proper amount of the mixture into each mould, putting the mixture together with the mould into an oven, heating for 60min at 200 ℃, and taking out the mixture after natural cooling; the product and the mould are put into hot deionized water for repeated soaking until NaCl is completely dissolved, and finally PVDF-HFP foam is obtained;
(2) 5 mmole of CuCl 2 ·2H 2 O, 2.5mmol NiCl 2 ·6H 2 O, 12mmol of urea and 10.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 10h at 100 ℃, and finally flushing the PVDF-HFP foam with deionized water and ethanol to obtain Cu 5 Ni 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
Example 10
70g of NaCl was weighed and put into a ball mill, and the ball-to-material ratio was 20 at a rotation speed of 100 rpm: 1, ball milling for 50 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; adding 10g PVDF-HFP powder, fully grinding uniformly to obtain a mixture, transferring the mixture into a mould with proper size, putting a proper amount of the mixture into each mould, putting the mixture together with the mould into an oven, heating for 30min at 200 ℃, and taking out the mixture after natural cooling; the product and the mould are put into hot deionized water for repeated soaking until NaCl is completely dissolved, and finally PVDF-HFP foam is obtained;
(2) 5 mmole of CuCl 2 ·2H 2 O, 2.5mmol FeCl 3 ·6H 2 O, 12mmol of urea and 20.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 10h at 100 ℃, and finally flushing the PVDF-HFP foam with deionized water and ethanol to obtain Cu 5 Fe 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
Example 11
50g of NaCl was weighed and put into a ball mill at a rotation speed of 500rpm and a ball-to-material ratio of 5:1 ball milling for 10 hours under the condition of 1 to obtain NaCl powder with uniform micron-sized size; adding 10g PVDF-HFP powder, fully grinding uniformly to obtain a mixture, transferring the mixture into a mould with proper size, putting a proper amount of the mixture into each mould, putting the mixture together with the mould into an oven, heating for 30min at 200 ℃, and taking out the mixture after natural cooling; the product and the mould are put into hot deionized water for repeated soaking until NaCl is completely dissolved, and finally PVDF-HFP foam is obtained;
(2) 5mmolFeCl 3 ·6H 2 O, 2.5mmol NiCl 2 ·6H 2 O, 12mmol of urea and 18.0mmolNH 4 F, dissolving the mixture in 60ml of deionized water together to form a mixed solution; taking PVDF-HFP foam obtained in the step (1), soaking the PVDF-HFP foam in the mixed solution for 30min after being completely wetted by ethanol, transferring the PVDF-HFP foam into a reaction kettle, reacting for 10h at 100 ℃, and finally flushing the PVDF-HFP foam with deionized water and ethanol to obtain Fe 5 Ni 2.5 LDHs (F) @ PVDF-HFP composite porous foam.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. The LDHs (F) @ PVDF-HFP composite porous foam material is characterized in that the foam material takes PVDF-HFP foam with adjustable pore canal size as a carrier, and the LDHs (F) is loaded on the PVDF-HFP foam in an array form; the preparation method of the LDHs (F) @ PVDF-HFP composite porous foam material 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 the mold after natural cooling; repeatedly soaking the material and the mould in deionized water to obtain PVDF-HFP foam;
(2) Metal salt A, metal salt B, urea and NH 4 F, jointly dissolving in deionized water to form a mixed solution; the PVDF-HFP foam obtained in the step (1) is fully wetted by ethanol, soaked in a mixed solution for a period of time, transferred to a reaction kettle for reaction, and washed by deionized water and ethanol to obtain the LDHs (F) @ PVDF-HFP composite porous foam material, wherein the mass ratio of PVDF-HFP to NaCl powder in the step (1) is 1: 5-9; in the step (2), the metal salt A is CoCl 2 ·6H 2 O、FeCl 3 ·6H 2 O or CuCl 2 ·2H 2 O; the metal salt B is FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O or NiCl 2 ·6H 2 O; the ratio relationship of the metal salt A, the metal salt B, urea, ammonium fluoride and deionized water is 5mmol: 1-5 mmol:12mmol: 4-20 mmol:60mL.
2. The preparation method of the 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 the mold after natural cooling; repeatedly soaking the material and the mould in deionized water to obtain PVDF-HFP foam;
(2) Metal salt A, metal salt B, urea and NH 4 F, jointly dissolving in deionized water to form a mixed solution; the PVDF-HFP foam obtained in the step (1) is fully wetted by ethanol, soaked in a mixed solution for a period of time, transferred to a reaction kettle for reaction, and washed by deionized water and ethanol to obtain the LDHs (F) @ PVDF-HFP composite porous foam material, wherein the mass ratio of PVDF-HFP to NaCl powder in the step (1) is 1: 5-9; in the step (2), the metal salt A is CoCl 2 ·6H 2 O、FeCl 3 ·6H 2 O or CuCl 2 ·2H 2 O; the metal salt B is FeCl 3 ·6H 2 O、CuCl 2 ·2H 2 O or NiCl 2 ·6H 2 O; the ratio relationship of the metal salt A, the metal salt B, urea, ammonium fluoride and deionized water is 5mmol: 1-5 mmol:12mmol: 4-20 mmol:60mL.
3. The preparation method of claim 2, wherein in the step (1), the rotation speed of the ball mill is 100-500 rpm, the ball milling time is 10-50 h, and the ball-to-material ratio is 5-20: 1.
4. the method of claim 2, wherein the milling in step (1) is for a period of at least 30 minutes; the heating temperature is 200deg.C, and the heating time is 30-60min.
5. The method of claim 2, wherein the PVDF-HFP foam in step (1) has a pore size of 300-500 microns.
6. 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.
7. 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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