CN111215140A - High-molecular composite membrane material with photocatalytic activity and preparation method thereof - Google Patents

High-molecular composite membrane material with photocatalytic activity and preparation method thereof Download PDF

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CN111215140A
CN111215140A CN201911250475.5A CN201911250475A CN111215140A CN 111215140 A CN111215140 A CN 111215140A CN 201911250475 A CN201911250475 A CN 201911250475A CN 111215140 A CN111215140 A CN 111215140A
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solution
polymer composite
spinning
zinc oxide
zinc
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张静
杨癸
马东伟
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Anyang Normal University
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Anyang Normal University
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    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J35/59—
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F6/46—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 of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D01F6/52—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 of polymers of unsaturated carboxylic acids or unsaturated esters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge

Abstract

The invention relates to the technical field of photocatalysis, in particular to a high-molecular composite membrane material with photocatalytic activity and a preparation method thereof, and the preparation method comprises the following steps: s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B to obtain a spinning solution; s2: performing electrostatic spinning on the spinning solution obtained in the step S1, and performing high-temperature heat treatment to obtain a nano zinc oxide/high polymer composite film; s3: and (3) etching the nano zinc oxide/polymer composite film prepared by S2 by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film. The modified nano zinc oxide and erbium oxide and neodymium oxide generated by the hydrolysis of the surface of the film have synergistic effect, so that the polymer composite film material has excellent photocatalytic activity.

Description

High-molecular composite membrane material with photocatalytic activity and preparation method thereof
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a high-molecular composite membrane material with photocatalytic activity and a preparation method thereof.
Background
With the increasing importance of the country and government on environmental protection, the topic of environmental governance is receiving wide attention. The photocatalytic material is widely applied due to the catalytic degradation of harmful substances in the wastewater to a certain degree, wherein inorganic oxides such as nano zinc oxide, nano titanium dioxide and other nano materials play an important role in the fields of textile, coating, wastewater treatment and the like due to the characteristics of excellent photocatalytic performance, good stability, large specific surface area and the like. However, the response range of the nano zinc oxide and the titanium dioxide to light is in the ultraviolet region, the nano zinc oxide and the titanium dioxide cannot play a photocatalysis role in the visible light range to degrade dirt, and photo-generated electrons and holes generated under the illumination condition are easy to be compounded, so that the two factors limit the application of the nano zinc oxide and the titanium dioxide to a certain extent.
Inorganic oxides such as nano zinc oxide, nano titanium dioxide and the like are modified to enable other elements to enter between crystal lattices, so that the response range of the elements to illumination can be extended to a visible light region, in addition, photo-generated electrons and holes can be effectively separated, and the photocatalytic activity of the elements is improved. The direct application of inorganic oxide or its aqueous dispersion in sewage treatment results in poor recoverability and resource waste, and the inorganic oxide or its aqueous dispersion is generally applied to a film
At present, the traditional photocatalytic composite film usually adopts a direct coating process, on one hand, the photocatalyst is unevenly loaded and is easy to agglomerate, on the other hand, the photocatalyst has poor stability in the film, and the thermal stability of the film is poor, so that the photocatalytic activity of the photocatalytic film is influenced, and therefore, the development of the photocatalytic composite film with good stability and good photocatalytic activity is needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to endow the antibacterial compound with excellent broad-spectrum antibacterial activity by adding the zinc-doped graphene quantum dots into the antibacterial polymer matrix in an in-situ blending mode and by using the graphene quantum dots, zinc ions, imidazole groups and hydrophobic fluorine-containing monomers in the system, and the antibacterial compound is not easy to migrate and volatilize, long-acting and durable in antibacterial effect, small in toxicity and good in biocompatibility.
In order to achieve the above object, the technical solution of the present invention is as follows.
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B in a mass ratio of 1-2: 1 to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film.
Preferably, the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
Preferably, in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
Preferably, in S1, the solution a includes the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
Preferably, the constant conditions of the electrospinning in S2 are: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
Preferably, in S2, the temperature of the heat treatment is 180-200 ℃ and the time is 1-1.5 h.
Preferably, in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate; the polymer composite film material also comprises 1-2 parts of soluble erbium salt and 1-2 parts of soluble neodymium salt by weight.
Preferably, in S3, the calcination process is performed as follows:
firstly, calcining at 100-180 ℃ for 3-6 h; then, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
The invention also provides a polymer composite membrane material with photocatalytic activity, which is prepared according to the preparation method.
The invention has the beneficial effects that:
(1) according to the method, the rare earth element europium is used for carrying out in-situ doping modification on the nano zinc oxide generated by hydrolyzing the zinc source precursor, so that the response range of the nano zinc oxide to illumination can be prolonged to a visible light region, photo-generated electrons and holes can be separated, and the photocatalytic activity of the nano zinc oxide is improved.
(2) The invention prepares the high molecular composite membrane by electrostatic spinning, which is beneficial to improving the stability of the nano zinc oxide in the membrane material.
(3) According to the invention, erbium salt and neodymium salt are hydrolyzed and deposited on the surface of the film through plasma etching treatment, and the film is endowed with excellent photocatalytic activity through the synergistic effect of the modified nano zinc oxide and erbium oxide and neodymium oxide generated by the hydrolysis of the surface of the film.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, but it should be understood that the scope of the present invention is not limited by the specific embodiments. The test methods not specified in the following examples are generally conducted under conventional conditions, and the sources of the test materials not specified are commercially available, and the steps thereof will not be described in detail since they do not relate to the invention.
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B according to a proportion to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning under a constant condition, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through high-temperature heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and then carrying out low-temperature treatment and high-temperature calcination to obtain the nano zinc oxide/polymer composite film.
Preferably, the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
Preferably, in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
Preferably, in S1, the solution a includes the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
Preferably, the ratio of solution a to solution B in S2 is 1: 1.
Preferably, the constant conditions of the electrospinning in S2 are: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
Preferably, the high temperature heat treatment in S2 is 180-200 ℃ for 1-1.5 h.
Preferably, in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate; the polymer composite film material also comprises 1-2 parts of soluble erbium salt and 1-2 parts of soluble neodymium salt by weight.
Preferably, in S3, the low-temperature treatment process is performed as follows: calcining at 100-180 ℃ for 3-6 h; the operation process of the high-temperature calcination treatment process is as follows: after the low temperature treatment is finished, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
Based on the same inventive concept, the invention also provides a polymer composite membrane material with photocatalytic activity, which is prepared by the preparation method.
The following examples are specifically included.
Example 1
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 60g of polylactic acid in 30g N, N-dimethylformamide solution, and stirring to obtain solution A; 1g of europium nitrate and 6g of zinc acetate are dispersed in 30g of acetone solution to obtain solution B; mixing the prepared solution A and the prepared solution B according to the mass ratio of 1:1 to obtain a spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 25 ℃, the environmental humidity is 30%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 10kV, a spinning solution advancing speed of 0.02mL/h and a receiving distance of 10cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by processing at 180 ℃ for 1 h;
s3: and (2) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 1g of erbium nitrate or 1g of neodymium nitrate into the acetone solution, reacting for 1-2h, calcining for 3h at 100 ℃, then heating to 260 ℃ by a speed program of 5 ℃/min, and calcining for 1h at 260 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Example 2
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polymethyl methacrylate in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 2g of europium nitrate and 8g of zinc nitrate in 40g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 50 ℃, the environmental humidity is 40%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 20kV and a spinning solution advancing speed of 0.1mL/h and a receiving distance of 15cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by performing high-temperature heat treatment at 200 ℃ for 1.5 h;
s3: and (3) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 2g of erbium nitrate or 2g of neodymium nitrate, reacting for 1-2h, calcining for 6h at 180 ℃, then heating to 320 ℃ by a speed program of 10 ℃/min, and calcining for 2h at 320 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Example 3
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 70g of polystyrene in 35g of N, N-dimethylformamide solution, and stirring to obtain a solution A; 1.5g of europium nitrate and 7g of zinc chloride are dispersed in 35g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 30%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 15kV, a spinning solution advancing speed of 0.05mL/h and a receiving distance of 12cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 190 ℃ for 1.2 h;
s3: and (2) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 1.5g of erbium nitrate or 1.5g of neodymium nitrate into the acetone solution, reacting for 1-2h, calcining for 4h at 150 ℃, then heating to 280 ℃ by a program at a speed of 8 ℃/min, and calcining for 1.5h at 280 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Comparative example 1
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 60g of polylactic acid in 30g of N, N-dimethylformamide solution, and stirring to obtain solution A; 1g of europium nitrate and 6g of zinc acetate are dispersed in 30g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 25 ℃, the environmental humidity is 40%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 10kV, the advancing speed of the spinning solution is 0.02mL/h, the receiving distance is 10cm, a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 180 ℃ for 1 h.
Comparative example 2
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polymethyl methacrylate polymer material in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 8g of zinc nitrate in 40g of acetone solution to obtain a solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 50 ℃, the environmental humidity is 35%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 20kV, a spinning solution advancing speed of 0.1mL/h and a receiving distance of 15cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 200 ℃ for 1.5 h;
s3: and (3) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 2g of erbium nitrate or 2g of neodymium nitrate acetone solution, reacting for 1-2h, calcining for 6h at 180 ℃, and then heating to 320 ℃ by a program and calcining for 2h to obtain the nano zinc oxide/polymer composite membrane.
Comparative example 3
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polylactic acid in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 8g of zinc chloride in 40g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 25%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 15kV, the advancing speed of the spinning solution is 0.05mL/h, the receiving distance is 12cm, a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 190 ℃ for 1.2 h.
Comparative example 4
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polylactic acid in 40g of N, N-dimethylformamide solution, and stirring to obtain a spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 25%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 15kV, the advancing speed of the spinning solution of 0.05mL/h and the receiving distance of 12cm, and carrying out high-temperature heat treatment at 190 ℃ for 1.2h to obtain the nano zinc oxide/polymer composite membrane.
Evaluation of photocatalytic degradation Properties
The samples prepared in the above examples 1 to 3 and comparative examples 1 to 4 were subjected to photocatalytic degradation performance evaluation tests by the following methods:
preparing 5mg/L rhodamine B solution, adding 50mg of the prepared sample into the solution, adsorbing for 30min under dark condition, irradiating for 60min under 400W ultraviolet lamp, and testing absorbance of supernatant liquid at 553nm by using an ultraviolet spectrophotometer.
The degradation rate of the dye was calculated by the following formula:
r% (degradation rate) ═ C0-Ct)/C0*100％
In the above formula: c0Is the initial concentration of rhodamine B dye, CtRefers to the concentration of rhodamine B dye at a particular time.
The test results are shown in table 1.
TABLE 1 dye degradation rate test results (%)
Inspection item Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Rate of dye degradation 98.6 99.3 98.9 89.1 83.6 73.2 10.7
From the above results, it can be seen that in examples 1 to 3, since the rare earth element europium modifies the nano zinc oxide formed by hydrolysis of the zinc source precursor to improve its photocatalytic activity, and further erbium salt and neodymium salt are hydrolyzed and deposited on the surface of the film by plasma treatment, the modified nano zinc oxide and erbium oxide and neodymium oxide formed by hydrolysis of the surface of the film act synergistically to impart excellent photocatalytic activity to the film, and therefore the degradation efficiency for rhodamine B dye can be up to 98% or more.
Compared with the examples 1-3, the plasma etching deposition is carried out without adding soluble erbium salt and soluble neodymium salt in the comparative example 1, the photocatalytic activity is lower than that of the examples 1-3, and the degradation efficiency is 89.1%;
in comparative example 2, europium nitrate is not added, and the europium nitrate and the zinc source precursor are hydrolyzed simultaneously in S1 to modify the generated nano zinc oxide, so that the photocatalytic activity of the nano zinc oxide is lower than that of examples 1-3, and the degradation efficiency is 83.6%;
comparative example 3 no europium source was added in S1 and no soluble erbium salt and soluble neodymium salt were plasma etch deposited in S3, thus the photocatalytic activity was lower than that of examples 1-3, and the degradation efficiency was 73.2%;
comparative example 4 was a composite film obtained by electrospinning only a polymer material without adding a zinc source, europium nitrate, a soluble erbium salt and a soluble neodymium salt, and thus, its photocatalytic activity was lower than that of examples 1 to 3, its degradation efficiency was 10.7%, and it had substantially no photocatalytic degradation activity.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. A preparation method of a high-molecular composite membrane material with photocatalytic activity is characterized by comprising the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B in a mass ratio of 1-2: 1 to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film.
2. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
3. The method of claim 1, wherein in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
4. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein in S1, the solution a comprises the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
5. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein the electrostatic spinning conditions in S2 are as follows: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
6. The method as claimed in claim 1, wherein the heat treatment temperature in S2 is 180-200 ℃ and the time is 1-1.5 h.
7. The method according to claim 1, wherein in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate.
8. The method according to claim 7, wherein the polymer composite film material further comprises 1-2 parts by weight of soluble erbium salt and 1-2 parts by weight of soluble neodymium salt.
9. The method according to claim 1, wherein the calcination process in S3 is performed as follows:
firstly, calcining at 100-180 ℃ for 3-6 h; then, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
10. A polymer composite membrane material with photocatalytic activity prepared by the preparation method according to any one of claims 1 to 9.
CN201911250475.5A 2019-12-09 2019-12-09 High-molecular composite membrane material with photocatalytic activity and preparation method thereof Pending CN111215140A (en)

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CN113351233A (en) * 2021-04-09 2021-09-07 南通大学 Tetracycline purification fiber membrane and preparation method thereof
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