CN113046856A - Preparation method of piezoelectric photocatalytic composite fiber with high cycle stability - Google Patents
Preparation method of piezoelectric photocatalytic composite fiber with high cycle stability Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
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- D—TEXTILES; PAPER
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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Abstract
The invention discloses a preparation method of a piezoelectric photocatalytic composite fiber with high cycle stability, which comprises the following steps: firstly, uniformly mixing a piezoelectric polymer, an organic solvent and an organic salt to form a spinning solution, and carrying out electrospinning and ultrasonic treatment to obtain a piezoelectric polymer fiber membrane; and then dripping the seed solution on the surface of the piezoelectric polymer fiber membrane, drying, then dripping the reaction solution on the surface of the fiber membrane, drying, repeatedly dripping for 5 times to obtain the piezoelectric polymer fiber with the photocatalyst seed crystal, finally putting the piezoelectric polymer fiber into a photocatalyst precursor and a hydrothermal solution, carrying out hydrothermal reaction, cleaning and drying to obtain the piezoelectric polymer composite fiber membrane with high cycle stability. The method can obtain the reusable piezoelectric photocatalytic composite fiber with high piezoelectric performance and high binding force, and has wide application prospects in the fields of sewage treatment, air purification, antibiosis and sterilization, hydrogen production by photolysis and the like.
Description
Technical Field
The invention belongs to the technical field of composite fiber preparation, and particularly relates to a preparation method of a piezoelectric photocatalytic composite fiber with high cycle stability.
Background
With the rapid development of social economy and the continuous increase of population, the solution of the problems of environmental pollution and energy shortage is particularly urgent, so that people can widely research stable, efficient, nontoxic, harmless and environment-friendly semiconductor photocatalytic materials. However, when the photocatalyst is used alone, the sunlight utilization rate is low, and photo-generated electrons and holes are easy to recombine, are easy to run off and are not beneficial to recycling, and the like. Researches show that the piezoelectric material can enhance the separation of carriers, reduce the recombination of the carriers and improve the catalytic performance of the photocatalyst. The piezoelectric polymer fiber has piezoelectric effect, can convert mechanical energy into electric energy to form electric field inside, and has the advantages of great specific surface area, low cost, simple process, easy doping modification, etc. The electrostatic spinning technology is one of effective modes for preparing the one-dimensional nanofibers, hygroscopic salt is added into spinning solution for preparing the polymer fibers, water molecules can be kept in the fibers, hydrogen atoms in the water molecules and fluorine atoms in PVDF form hydrogen bonds to facilitate the formation of beta phases and improve the piezoelectric performance of the polymers, a polymer fiber membrane with a special structure can be obtained through post-treatment, and a photocatalyst can be fixed, so that the photocatalytic efficiency and the reusability of the photocatalyst are improved. Therefore, it is necessary to prepare the piezoelectric photocatalytic composite fiber with self-polarization and high cycle stability.
Wu et al (Wen Wu, Xin Yin, et al. Water flow driven piezo-photocatalytic flexible films: Bi-piezo electric integration of ZnO nanoparticles and PVDF [ J ]. Applied Surface Science 517(2020)146119.) prepared a ZnO @ PVDF photocatalytic composite film with a high polarity Surface (100) by hydrothermal method in combination with spin coating method, although the increase of the ZnO polarity Surface improves the piezoelectric property of the composite film and the photocatalytic property is improved, the photocatalyst has a serious coating phenomenon, so the improvement of the photocatalytic property is limited.
Chinese patent "preparation method of polyvinylidene fluoride/titanium dioxide composite nanofiber membrane" (application No. CN201110450301.0, application publication No. CN102704190A, published: 2012-10-03) discloses that a method combining sol-gel, electrostatic spinning and solvothermal method is adopted to prepare polyvinylidene fluoride/titanium dioxide composite nanofiber, a titanium dioxide precursor is added into a spinning solution, then titanium dioxide particles are grown on the surfaces of the fibers, the composite nanofiber has a large specific surface area and high photocatalytic activity, however, a photocatalyst is only combined with a matrix on the surfaces, and the composite nanofiber is easy to fall off and run off.
Chinese patent "a PVDF/hexagonal prism shaped ZnO nanowire fiber membrane and its preparation method and use" (application number: CN201811645417.8, application publication number: CN109731613A, published date: 2019-05-10) discloses that the PVDF/hexagonal prism shaped ZnO nanowire fiber membrane is prepared by electrostatic spinning method and hydrothermal treatment, the nanowire grows on the surface of the membrane to improve the specific surface area, and higher photocatalysis efficiency is obtained, however, the nanowire and the matrix fiber are easy to fall off in a surface combination mode, and the repeated reutilization is not facilitated.
Chinese patent PVDF/TiO2A composite photocatalytic film, its preparation method, its application and its repairing method (application No. CN202010848946.9, application publication No. CN111905811A, publication No. 2020-11-10) disclose PVDF and TiO dissolved in a glass plate2Forming the DMF mixed solution of the powder, and then soaking the powder in deionized water to obtain PVDF/TiO with pores2The composite photocatalytic film has pores, and can improve the activity of photocatalyst and increase the TiO content of photocatalyst2The contact area of the catalyst and the degradation product improves the degradation efficiency. However, most of the TiO in this process2The powder is wrapped in the matrix to limit TiO2The photocatalytic efficiency cannot be greatly improved due to the photocatalytic effect of the photocatalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a piezoelectric photocatalytic composite fiber with high cycle stability, and solves the problem of weak surface bonding of the composite fiber in the prior art.
The technical scheme adopted by the invention is that the preparation method of the piezoelectric photocatalytic composite fiber with high cycle stability is implemented according to the following steps:
step 3, carrying out ultrasonic treatment on the piezoelectric polymer fiber membrane by using an ultrasonic cleaning machine, removing organic salt on the surface of the nanofiber, and drying to obtain the piezoelectric polymer fiber membrane with a recess structure;
step 4, dripping the seed solution on the surface of the piezoelectric polymer fiber membrane with the recess structure, drying for 3min at 120 ℃, then dripping the reaction solution on the surface of the piezoelectric polymer fiber membrane, drying for 3min at 120 ℃, repeatedly and alternately dripping the seed solution and the reaction solution for 5 times to obtain the piezoelectric polymer fiber with the photocatalyst seed crystal;
and 5, putting the piezoelectric polymer fiber with the photocatalyst seed crystals into a mixed solution of a photocatalyst precursor and a hydrothermal solution, carrying out hydrothermal reaction, cleaning with a cleaning agent, and drying to obtain the piezoelectric polymer composite fiber membrane with high cycle stability.
The present invention is also characterized in that,
in the step 1, the piezoelectric polymer is any one of poly (vinylidene fluoride-trifluoroethylene), polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene; the organic salt is tetrabutyl ammonium chloride; the organic solvent is prepared from the following components in a mass ratio of 7: 3, and acetone.
In step 2, the spinning parameters are as follows: the spinning voltage is 15-30 kv, the receiving distance is 15-20 cm, the spinning temperature is 25-30 ℃, the spinning humidity is 20-30%, the propelling speed of the propulsion pump is 0.8-1 mL/h, and the spinning time is 2-3 h.
In the step 3, the ultrasonic frequency is 45kHz, the ultrasonic temperature is 40 ℃, and the ultrasonic time is 3 h.
In step 4, the seed solution is formed by mixing a catalytic substance and absolute ethyl alcohol; the concentration of the seed solution is 0.1mol/L-0.5 mol/L; the catalyst is any one of butyl titanate, zinc acetate, chromium nitrate and nickel nitrate; the reaction solution is hydrochloric acid or sodium hydroxide solution.
In the step 5, the hydrothermal reaction temperature is 90-180 ℃, and the hydrothermal reaction time is 4-6 h; the drying temperature is 60 ℃ and the drying time is 4 h.
In the step 5, the photocatalyst precursor is any one of butyl titanate, titanium chloride, zinc acetate, nickel nitrate, zinc nitrate and chromium nitrate; the hydrothermal solution is one or a mixed solution of two of deionized water, hexamethylenetetramine, hydrochloric acid, thiourea, hexamethylenediamine, urea and absolute ethyl alcohol; the cleaning agent is one or two of deionized water and absolute ethyl alcohol.
The invention has the beneficial effects that: the method can obtain the reusable piezoelectric photocatalytic composite fiber with high piezoelectric performance and high bonding force. Firstly, an organic salt TBAC in the spinning solution is a hygroscopic salt, water can be retained in the fiber, and hydrogen bonds formed between hydrogen atoms in water molecules and fluorine atoms in PVDF are favorable for forming a beta phase, so that the piezoelectric property of the fiber is improved, a stronger internal electric field is obtained, and the separation of photo-generated electrons and holes is effectively driven; TBAC on the surface of the fiber can be removed through a simple water washing process, and a recess structure is formed on the surface of the fiber, so that conditions are provided for formation and growth of photocatalyst seed crystals and fixation of nanorods; adjusting the dipping process to control the concentration of the seed solution to ensure that the solution nucleates in the recess to obtain photocatalyst seed crystals so as to promote the selective growth of the photocatalyst in the subsequent treatment; by controlling the hydrothermal time and temperature in hydrothermal treatment, photocatalyst nanorods formed by seed crystal growth are tightly rooted in the recess, so that the reusable piezoelectric photocatalytic composite fiber with high piezoelectric property and high binding force is obtained, and the piezoelectric photocatalytic composite fiber has wide application prospects in the fields of sewage treatment, air purification, antibiosis and sterilization, hydrogen production by photolysis of water and the like.
Drawings
FIG. 1 is a schematic diagram of the shape of a single piezoelectric photocatalytic composite fiber prepared by the method and a local enlarged longitudinal section.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a piezoelectric photocatalytic composite fiber with high cycle stability, which is implemented by the following steps:
weighing the following components in percentage by mass: 16-20% of piezoelectric polymer, 1-2% of organic salt and 78-83% of organic solvent, wherein the sum of the mass percentages of the components is 100%; mixing a piezoelectric polymer, an organic solvent and an organic salt, and uniformly stirring to form a spinning solution;
the piezoelectric polymer is any one of poly (vinylidene fluoride-trifluoroethylene) (P (VDF-TrFE)), polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP);
the organic salt is tetrabutyl ammonium chloride (TBAC);
the organic solvent is prepared from the following components in a mass ratio of 7: 3, N-Dimethylformamide (DMF) and acetone;
the spinning parameters are as follows: the spinning voltage is 15-30 kv, the receiving distance is 15-20 cm, the spinning temperature is 25-30 ℃, the spinning humidity is 20-30%, the propelling speed of the propulsion pump is 0.8-1 mL/h, and the spinning time is 2-3 h;
step 3, carrying out ultrasonic treatment on the piezoelectric polymer fiber membrane by using an ultrasonic cleaning machine to remove TBAC on the surface of the nanofiber, and then drying for 4 hours at the temperature of 60 ℃ to obtain the piezoelectric polymer fiber membrane with a recess structure;
the ultrasonic frequency is 45kHz, the ultrasonic temperature is 40 ℃, and the ultrasonic time is 3 h;
step 4, dripping a seed solution with the concentration of 0.1-0.5 mol/L onto the surface of the piezoelectric polymer fiber membrane with a recess structure, drying for 3min at 120 ℃, then dripping a reaction solution onto the surface of the piezoelectric polymer fiber membrane, drying for 3min at 120 ℃, repeatedly and alternately dripping the seed solution and the reaction solution for 5 times, and obtaining the piezoelectric polymer fiber with the photocatalyst seed crystals by nucleation in the recesses;
wherein the seed solution is formed by mixing a catalytic substance and absolute ethyl alcohol;
the catalyst is any one of butyl titanate, zinc acetate, chromium nitrate and nickel nitrate;
the reaction solution is hydrochloric acid or sodium hydroxide solution;
the concentration of the sodium hydroxide solution is 1 mol/L; the mass fraction of the hydrochloric acid is 36 percent;
and 5, putting the piezoelectric polymer fiber with the photocatalyst seed crystal obtained in the step 4 into a mixed solution of a photocatalyst precursor and a hydrothermal solution, carrying out hydrothermal reaction, then cleaning with a cleaning agent, and drying to obtain the piezoelectric polymer composite fiber membrane with high cycle stability.
The hydrothermal reaction temperature is 90-180 ℃, and the hydrothermal reaction time is 4-6 h;
the drying temperature is 60 ℃, and the drying time is 4 hours;
the photocatalyst precursor is any one of butyl titanate, titanium chloride, zinc acetate, nickel nitrate, zinc nitrate and chromium nitrate;
the hydrothermal solution is one or a mixed solution of two of deionized water, hexamethylenetetramine, hydrochloric acid, thiourea, hexamethylenediamine, urea and absolute ethyl alcohol;
the cleaning agent is one or two of deionized water and absolute ethyl alcohol;
according to the method, hygroscopic organic salt tetrabutylammonium chloride (TBAC) is added into the spinning solution, so that moisture can be retained in the fiber, and hydrogen bonds formed between hydrogen atoms in water molecules and fluorine atoms in PVDF are favorable for forming beta phase, so that the piezoelectric property of the fiber is improved, a stronger internal electric field is obtained, and the separation of photo-generated electrons and holes is effectively driven; TBAC on the surface of the fiber can be removed through a simple water washing process, and a recess structure is formed on the surface of the fiber, so that conditions are provided for formation and growth of photocatalyst seed crystals and fixation of nanorods; adjusting the dipping process to control the concentration of the seed solution to ensure that the solution nucleates in the recess to obtain photocatalyst seed crystals so as to promote the selective growth of the photocatalyst in the subsequent treatment; by controlling the hydrothermal time and temperature in hydrothermal treatment, photocatalyst nanorods formed by seed crystal growth are tightly rooted in the recess, and the piezoelectric photocatalytic composite fiber with high circulation stability is obtained.
The invention prepares the reusable piezoelectric photocatalytic composite fiber with high piezoelectric property and high bonding force by an electrostatic spinning method and corresponding post-treatment. The photocatalyst nanorods are rooted in a cavity structure of the high beta-phase PVDF electrospun fiber membrane, and the piezoelectric photocatalytic composite fiber has better circulation stability, so that the piezoelectric photocatalytic composite fiber has wide application prospects in the fields of sewage treatment, air purification, antibiosis and sterilization, hydrogen production by photolysis of water and the like.
EXAMPLE 1 preparation of PVDF-TiO2Nano-rod piezoelectric photocatalytic composite fiber
2.397g of PVDF powder was added to a mixed solution of 10ml of N, N-Dimethylformamide (DMF) and 4ml of acetone, and stirred in a water bath at 40 ℃ for 4 hours to prepare a PVDF solution with a mass fraction of 16%. After sufficient dissolution, 1.5g tetrabutylammonium chloride was added and stirring was continued for 1h to obtain a spinning solution. Injecting a certain volume of spinning solution into a needle cylinder, adjusting the spinning voltage to be 25kv, the receiving distance to be 15cm, the spinning temperature to be 28 ℃, the humidity to be 30%, the propelling speed of a propelling pump to be 0.8mL/h, and performing electrostatic spinning for 2h to obtain the PVDF high-voltage fiber membrane.
And (2) washing the high-voltage electric fiber membrane, carrying out ultrasonic treatment on the PVDF/TBAC nano fiber membrane by using an ultrasonic cleaner to remove TBAC on the surface of the nano fiber, wherein the ultrasonic frequency is 45kHz, the water bath temperature is 40 ℃, the treatment time is 3 hours, and drying for 4 hours at the temperature of 60 ℃ to obtain the piezoelectric polymer fiber membrane with the recess structure.
And (3) carrying out impregnation treatment on the obtained piezoelectric polymer fiber membrane, dripping a tetrabutyl titanate seed solution with the concentration of 0.1mol/L onto the surface of the fiber membrane, drying at 120 ℃ for 3 minutes, dripping a hydrochloric acid solution with the mass fraction of 36% onto the surface of the fiber, drying at 120 ℃ for 3 minutes, and repeating the process for 5 times to obtain the piezoelectric polymer fiber with photocatalyst seed crystals.
Then carrying out hydrothermal treatment on the piezoelectric polymer fiber with the photocatalyst seed crystal, dissolving 1.322g of titanium tetrachloride in 50ml of hydrochloric acid with the mass fraction of 36% and 50ml of deionized water, transferring the solution into a reaction kettle, the volume of the solution is 80% of that of the reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 4 hours, cooling to room temperature, washing a sample with deionized water and absolute ethyl alcohol for several times, and then drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer composite film with high cycling stability.
Example 2 preparation of PVDF-ZnO nanorod piezoelectric photocatalytic composite fiber
2.397g of PVDF powder was added to a mixed solution of 10ml of N, N-Dimethylformamide (DMF) and 4ml of acetone, and stirred in a water bath at 40 ℃ for 4 hours to prepare a PVDF solution with a mass fraction of 16%. After the solution was sufficiently dissolved, 3g of tetrabutylammonium chloride was added and stirring was continued for 2 hours to obtain a spinning solution. Injecting a certain volume of spinning solution into a needle cylinder, adjusting the spinning voltage to be 30kv, the receiving distance to be 15cm, the spinning temperature to be 25 ℃, the humidity to be 30%, the propelling speed of a propelling pump to be 1mL/h, and performing electrostatic spinning for 2h to obtain the PVDF high-voltage fiber membrane.
And (2) washing the high-voltage electric fiber membrane, carrying out ultrasonic treatment on the PVDF/TBAC nano fiber membrane by using an ultrasonic cleaner to remove TBAC on the surface of the nano fiber, wherein the ultrasonic frequency is 45kHz, the water bath temperature is 40 ℃, the treatment time is 3 hours, and drying for 4 hours at the temperature of 60 ℃ to obtain the piezoelectric polymer fiber membrane with the recess structure.
And (3) carrying out impregnation treatment on the obtained piezoelectric polymer fiber membrane, dripping a zinc acetate seed solution with the concentration of 0.1mol/L onto the surface of the fiber membrane, drying at 120 ℃ for 3 minutes, dripping 1mol/L sodium hydroxide onto the surface of the fiber, drying at 120 ℃ for 3 minutes, and repeating the process for 5 times to obtain the piezoelectric polymer fiber with photocatalyst seed crystals.
Then carrying out hydrothermal treatment on the piezoelectric polymer fiber with the photocatalyst seed crystal, dissolving 0.849g of zinc acetate and 0.701g of hexamethylenetetramine in 100ml of deionized water, transferring the solution into a reaction kettle, wherein the volume of the solution is 80% of that of the reaction kettle, carrying out hydrothermal treatment at 90 ℃ for 6 hours, cooling to room temperature, washing a sample with absolute ethyl alcohol and deionized water for a plurality of times, and drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer composite film with high cycle stability.
Example 3 preparation of PVDF-CdS nanorod piezoelectric photocatalytic composite fiber
2.762g of PVDF powder is added into a mixed solution of 10ml of N, N-Dimethylformamide (DMF) and 4ml of acetone, and stirred in a water bath at 40 ℃ for 4 hours to prepare a PVDF solution with the mass fraction of 18 percent. After sufficient dissolution, 2.3g tetrabutylammonium chloride was added and stirring was continued for 1.5h to obtain a spinning solution. Injecting a certain volume of spinning solution into a needle cylinder, adjusting the spinning voltage to be 30kv, the receiving distance to be 20cm, the spinning temperature to be 30 ℃, the humidity to be 25%, the propelling speed of a propelling pump to be 1mL/h, and performing electrostatic spinning for 2h to obtain the PVDF high-voltage fiber membrane.
Washing the high-voltage electric fiber membrane with water, carrying out ultrasonic treatment on the PVDF/TBAC nano fiber membrane by adopting an ultrasonic cleaner, wherein the ultrasonic frequency is 45kHz, the water bath temperature is 40 ℃, the treatment time is 3 hours, removing TBAC on the surface of the nano fiber, and drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer fiber membrane with a recess structure.
And (3) carrying out impregnation treatment on the obtained piezoelectric polymer fiber membrane, dropwise adding a cadmium nitrate seed solution with the concentration of 0.2mol/L to the surface of the fiber membrane, drying at 120 ℃ for 3 minutes, then dropwise adding a sodium hydroxide solution with the concentration of 1mol/L to the surface of the fiber, drying at 120 ℃ for 3 minutes, and repeating the process for 5 times to obtain the piezoelectric polymer fiber with photocatalyst seed crystals.
Then carrying out hydrothermal treatment on the piezoelectric polymer fiber with the photocatalyst seed crystals, dissolving 3.84g of cadmium nitrate tetrahydrate and 2.84g of thiourea in 100ml of hexamethylenediamine to obtain a clear solution, transferring the clear solution into a reaction kettle, wherein the volume of the clear solution is 80% of that of the reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 6 hours, cooling to room temperature, washing a sample with absolute ethyl alcohol and deionized water for a plurality of times, and then drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer composite film with high cycle stability.
Example 4 preparation of PVDF-NiO nanorod piezoelectric photocatalytic composite fiber
3.146g of PVDF powder is added into a mixed solution of 10ml of N, N-Dimethylformamide (DMF) and 4ml of acetone, and stirred in a water bath at 40 ℃ for 4 hours to prepare a PVDF solution with the mass fraction of 20%. After sufficient dissolution, 2.3g tetrabutylammonium chloride was added and stirring was continued for 1.5h to obtain a spinning solution. Injecting a certain volume of spinning solution into a needle cylinder, adjusting the spinning voltage to be 28kv, the receiving distance to be 18cm, the spinning temperature to be 25 ℃, the humidity to be 20%, the propelling speed of a propelling pump to be 0.8mL/h, and performing electrostatic spinning for 3h to obtain the PVDF high-voltage fiber membrane.
Washing the high-voltage electric fiber membrane with water, carrying out ultrasonic treatment on the PVDF/TBAC nano fiber membrane by adopting an ultrasonic cleaner, wherein the ultrasonic frequency is 45kHz, the water bath temperature is 40 ℃, the treatment time is 3 hours, removing TBAC on the surface of the nano fiber, and drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer fiber membrane with a recess structure.
And (3) carrying out impregnation treatment on the obtained piezoelectric polymer fiber membrane, dropwise adding a nickel nitrate seed solution with the concentration of 0.5mol/L to the surface of the fiber membrane, drying at 120 ℃ for 3 minutes, then dropwise adding a sodium hydroxide solution with the concentration of 1mol/L to the surface of the fiber, drying at 120 ℃ for 3 minutes, and repeating the process for 5 times to obtain the piezoelectric polymer fiber with photocatalyst seed crystals.
Then carrying out hydrothermal treatment on the piezoelectric polymer fiber with the photocatalyst seed crystal, dissolving 2.8g of nickel nitrate hexahydrate and 0.8g of urea in 100ml of deionized water, transferring the mixture into a reaction kettle, carrying out hydrothermal treatment at the volume of 80% of the reaction kettle for 5 hours at 120 ℃, cooling to room temperature, washing a sample for a plurality of times by using the deionized water and absolute ethyl alcohol, and drying at the temperature of 60 ℃ for 10 hours to obtain the piezoelectric polymer composite film with high cycling stability.
Example 5 preparation of PVDF-ZnO nanorod piezoelectric photocatalytic composite fiber
2.577g of PVDF powder was added to a mixed solution of 10ml of N, N-Dimethylformamide (DMF) and 4ml of acetone, and stirred in a water bath at 40 ℃ for 4 hours to prepare a PVDF solution with a mass fraction of 17%. After sufficient dissolution, 2.3g tetrabutylammonium chloride was added and stirring was continued for 1.5h to obtain a spinning solution. Injecting a certain volume of spinning solution into a needle cylinder, adjusting the spinning voltage to be 25kv, the receiving distance to be 16cm, the spinning temperature to be 26 ℃, the humidity to be 30%, the propelling speed of a propelling pump to be 1mL/h, and performing electrostatic spinning for 2h to obtain the PVDF high-voltage fiber membrane.
Washing the high-voltage electric fiber membrane with water, carrying out ultrasonic treatment on the PVDF/TBAC nano fiber membrane by adopting an ultrasonic cleaner, wherein the ultrasonic frequency is 45kHz, the water bath temperature is 40 ℃, the treatment time is 3 hours, removing TBAC on the surface of the nano fiber, and drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer fiber membrane with a recess structure.
And (3) carrying out dipping treatment on the obtained piezoelectric polymer fiber membrane, dripping a zinc acetate seed solution with the concentration of 0.3mol/L onto the surface of the fiber membrane, drying at 120 ℃ for 3 minutes, dripping a sodium hydroxide solution with the concentration of 1mol/L onto the surface of the fiber, drying at 120 ℃ for 3 minutes, and repeating the process for 5 times to obtain the piezoelectric polymer fiber with the photocatalyst seed crystals.
Then carrying out hydrothermal treatment on the piezoelectric polymer fiber with the photocatalyst seed crystals, dissolving 0.595g of zinc nitrate hexahydrate and 0.28g of hexamethylenetetramine in 100ml of deionized water, transferring the solution into a reaction kettle, wherein the volume of the solution is 80% of that of the reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 4 hours, cooling to room temperature, washing a sample with deionized water and absolute ethyl alcohol for a plurality of times, and then drying at 60 ℃ for 4 hours to obtain the piezoelectric polymer composite film with high cycling stability.
TABLE 1 PVDF-TiO from example 12Nano-rod piezoelectric photocatalytic composite fiber and non-cavity structure PVDF/TiO2And (3) comparing the degradation rate of the piezoelectric photocatalytic composite fiber to the photocatalytic methylene blue. As can be seen from Table 1, PVDF/TiO with no recessed structure2Piezoelectric photocatalytic composite fiber and PVDF/TiO in example 12PVDF/TiO composite fiber without recessed structure compared with piezoelectric photocatalysis composite fiber2The degradation rate of the piezoelectric photocatalytic composite fiber is obviously reduced after a plurality of cycles, while the PVDF-TiO composite fiber in the example 12The degradation rate of the nano-rod piezoelectric photocatalytic composite fiber is always in a higher level because the high beta-phase PVDF has higher piezoelectric performance, stronger internal electric field can be obtained to efficiently drive the separation of photon-generated carriers, the photocatalytic performance is improved, and simultaneously, root-implanted photocatalyst nano-rods grow in a cavity structure, so that the photocatalytic cycle stability of the composite fiber is greatly improved。
TABLE 1 degradation rate of piezoelectric photocatalytic composite fiber to photocatalytic methylene blue
FIG. 1 is a schematic diagram of the shape of a single piezoelectric photocatalytic composite fiber prepared by the method and a locally enlarged longitudinal section. Wherein, in the schematic diagram of the local enlarged longitudinal section morphology, 1 is a piezoelectric polymer fiber membrane, 2 is a photocatalyst nanorod, and 3 is a sink structure. As can be seen from FIG. 1, after impregnation and hydrothermal treatment, catalyst nanorods grow and are planted in the recessed structures on the fiber surface.
Claims (7)
1. A preparation method of a piezoelectric photocatalytic composite fiber with high cycle stability is characterized by comprising the following steps:
step 1, weighing the following components in percentage by mass: 16-20% of piezoelectric polymer, 1-2% of organic salt and 78-83% of organic solvent, wherein the sum of the mass percentages of the components is 100%; mixing a piezoelectric polymer, an organic solvent and an organic salt, and uniformly stirring to form a spinning solution;
step 2, carrying out electrospinning on the spinning solution prepared in the step 1 to obtain a piezoelectric polymer fiber membrane;
step 3, carrying out ultrasonic treatment on the piezoelectric polymer fiber membrane by using an ultrasonic cleaning machine, removing organic salt on the surface of the nanofiber, and drying to obtain the piezoelectric polymer fiber membrane with a recess structure;
step 4, dripping the seed solution on the surface of the piezoelectric polymer fiber membrane with the recess structure, drying for 3min at 120 ℃, then dripping the reaction solution on the surface of the piezoelectric polymer fiber membrane, drying for 3min at 120 ℃, repeatedly and alternately dripping the seed solution and the reaction solution for 5 times to obtain the piezoelectric polymer fiber with the photocatalyst seed crystal;
and 5, putting the piezoelectric polymer fiber with the photocatalyst seed crystals into a mixed solution of a photocatalyst precursor and a hydrothermal solution, carrying out hydrothermal reaction, cleaning with a cleaning agent, and drying to obtain the piezoelectric polymer composite fiber membrane with high cycle stability.
2. The method for preparing a piezoelectric photocatalytic composite fiber with high cycle stability according to claim 1, wherein in the step 1, the piezoelectric polymer is any one of poly (vinylidene fluoride-trifluoroethylene), polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene; the organic salt is tetrabutyl ammonium chloride; the organic solvent is prepared from the following components in a mass ratio of 7: 3, and acetone.
3. The method for preparing the piezoelectric photocatalytic composite fiber with high cycling stability according to claim 1, wherein in the step 2, the spinning parameters are as follows: the spinning voltage is 15-30 kv, the receiving distance is 15-20 cm, the spinning temperature is 25-30 ℃, the spinning humidity is 20-30%, the propelling speed of the propulsion pump is 0.8-1 mL/h, and the spinning time is 2-3 h.
4. The preparation method of the piezoelectric photocatalytic composite fiber with high cycle stability according to claim 1, wherein in the step 3, the ultrasonic frequency is 45kHz, the ultrasonic temperature is 40 ℃, and the ultrasonic time is 3 h.
5. The method for preparing the piezoelectric photocatalytic composite fiber with high cycle stability according to claim 1, wherein in the step 4, the seed solution is formed by mixing a catalytic material and absolute ethyl alcohol; the concentration of the seed solution is 0.1mol/L-0.5 mol/L; the catalyst is any one of butyl titanate, zinc acetate, chromium nitrate and nickel nitrate; the reaction solution is hydrochloric acid or sodium hydroxide solution.
6. The method for preparing a piezoelectric photocatalytic composite fiber with high cycling stability according to claim 1, wherein in the step 5, the hydrothermal reaction temperature is 90 ℃ to 180 ℃, and the hydrothermal reaction time is 4 to 6 hours; the drying temperature is 60 ℃ and the drying time is 4 h.
7. The method for preparing the piezoelectric photocatalytic composite fiber with high cycle stability according to claim 1, wherein in the step 5, the photocatalyst precursor is any one of butyl titanate, titanium chloride, zinc acetate, nickel nitrate, zinc nitrate and chromium nitrate; the hydrothermal solution is one or a mixed solution of two of deionized water, hexamethylenetetramine, hydrochloric acid, thiourea, hexamethylenediamine, urea and absolute ethyl alcohol; the cleaning agent is one or two of deionized water and absolute ethyl alcohol.
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