CN112941643A - Method for preparing photocatalytic fiber through microfluid electrostatic spinning - Google Patents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
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- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a method for preparing a photocatalytic fiber by microfluid electrostatic spinning. The method is characterized in that: the polymer is dissolved in a solvent to prepare a uniform solution, the uniform solution is transferred to a needle tube, the microfluid electrostatic spinning is used for preparing fibers, and the fibers are subjected to in-situ polymerization by a photocatalytic material to form the photocatalytic fibers, so that the photocatalytic performance of the fibers can be greatly improved, and the conversion rate of carbon dioxide is increased. The invention does not need an external heating source to maintain the polymerization of the whole system in the spinning reaction process, has controllability, short spinning reaction time, energy saving and no pollution; the method provides a stable and efficient method for the rapid preparation of the photocatalytic fiber through in-situ synthesis, and has industrial prospect.
Description
Technical Field
The invention relates to the field of solar photocatalysis, designs a preparation technology of functional polymer fibers, and particularly relates to a method for preparing photocatalytic fibers by microfluid electrostatic spinning.
Background
Carbon dioxide (CO) in the atmosphere2) Has profound influence on the world climate system. In order to reduce carbon dioxide in the air, a great deal of research has been conducted on alternative energy systems that do not rely on fossil fuels as a primary source of energy. Among the various approaches that help solve this problem is the photocatalytic conversion of carbon dioxide to renewable fuels. The development of highly active, selective and stable photocatalysts is a key requirement for the development of practical carbon dioxide conversion processes under conditions as mild as possible. However, other requirements must also be met for the process to be commercially viable; such photocatalysts must be present in large numbers on earth, are low cost, non-toxic, and are capable of absorbing solar photons over a wide spectral range. The photocatalytic fiber can meet the conditions, but the currently developed photocatalytic fiber is generally high in cost, poor in stability, complex in preparation process and low in carbon monoxide yield, and the general yield is 10-20 mu mol g-1h-1. The existing market urgently needs a preparation method of the photocatalytic fiber with simple operation, low cost and good stability.
Disclosure of Invention
The invention provides a method for preparing photocatalytic fibers by microfluid electrostatic spinning in order to realize simple preparation of photocatalytic materials; the method has the advantages of high preparation speed, high efficiency, low cost, simple operation and the like, and the nanofiber photothermal composite material has excellent photocatalytic performance, and simultaneously the excellent fiber flexibility provides possibility for the design and preparation of the 3D photothermal absorption material with a unique shape, and has higher application value in industrial production.
The technical scheme of the invention is as follows: a method for preparing photocatalytic fibers by microfluid electrostatic spinning comprises the following specific steps:
(1) dissolving a polymer in a solvent, and fully dissolving to obtain a polymer spinning solution;
(2) adjusting the parameters of microfluid electrostatic spinning to carry out electrostatic spinning to prepare a uniform polymer fiber membrane;
(3) in-situ synthesis of the catalyst: mixing reactants and water in a reactor to form a solution, adjusting the pH value of the solution, then putting a polymer fiber membrane into the solution, putting the reactor into a reaction bath, dropwise adding an oxidant, and heating for in-situ growth; and then washing and drying to remove unreacted monomers and free particles to obtain the photocatalytic fiber.
Preferably, in the step (1), the polymer is one or a combination of polyamide 66, thermoplastic polyurethane, polyacrylonitrile, polycaprolactone, polyimide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl chloride and polyvinylidene fluoride; the solvent is one or more of formic acid, ethanol or N, N-dimethylformamide; the mass fraction of the polymer spinning solution is 10-20%.
Preferably, the parameters of the microfluid electrostatic spinning in the step (2) are as follows: the liquid inlet amount is 1-10mL h-1The voltage is 10-20kV, the environmental temperature is 20-35 ℃, and the environmental humidity is 55-65%.
Preferably, the reactant in the step (3) is one of copper sulfate, tetrabutyl titanate or pyrrole and a derivative thereof; the mass ratio of reactants to water is (1-5): 50.
preferably, the oxidant is one or the combination of glucose, ferric chloride or ferric sulfate; the mass ratio of the oxidant to the water is (1-3): 50.
preferably, the pH value in the step (3) is in the range of 8-14; the heating temperature of the reaction bath is 75-90 ℃, and the heating time is 0.5-3 hours.
Preferably, the washing solvent in the step (3) is ethanol, and the washing times are 2-10 times; the drying temperature is 40-60 ℃.
According to the invention, the high-strength polymer nanofiber membrane is prepared by a microfluid electrostatic spinning technology, and then is subjected to in-situ polymerization by a photocatalytic material to form the photocatalytic fiber, so that the photocatalytic performance of the fiber can be greatly improved, and the efficiency of carbon dioxide reduction is increased. The polymerization of the whole system is maintained without an external heating source in the spinning reaction process, so that the controllability is realized, the spinning reaction time is short, the energy is saved, and the pollution is avoided. Most importantly, the preparation method of the fiber membrane is simple, can realize large-scale production, and has industrial prospect.
Has the advantages that:
the invention combines the microfluid electrostatic spinning technology and the in-situ synthesis method to prepare the photocatalytic fiber with excellent photocatalytic performance, and has the following specific advantages:
(1) the synthesis method of the photocatalytic fiber prepared by the invention is simple, the used equipment is convenient to operate, and the used materials are green, safe and pollution-free.
(2) The photocatalytic fiber prepared by the method is prepared by a microfluid electrostatic spinning technology, and the size and microstructure of the nanofiber can be accurately regulated and controlled by the cooperative work of the microfluid technology and the electrostatic spinning technology, so that the tensile strength of the nanofiber is improved.
(3) The photocatalytic fiber prepared by the method has excellent carbon dioxide conversion performance, and the yield of carbon monoxide can reach 45.33 mu mol g-1h-1Has wide industrialization prospect and higher popularization and application values
Drawings
FIG. 1 is an SEM photograph of a photocatalytic fiber in example 1;
FIG. 2 is a graph showing the carbon monoxide yield of the photocatalytic fiber in example 1.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
Example 1: 10g of polyamide 66 are dissolved in 90g of 88% formic acid to form a spinning dope with a mass fraction of 10%. The dope system was loaded into a 20mL syringe fixed in a microflow pump. Setting the flow rate of the micro-flow pump to 1mL h-1. The voltage was set at 10kV and a thermoplastic polyurethane fiber film was obtained on the receiver. The morphology of the fiber is shown in FIG. 1, and the diameter of the fiber is about 200 nm. The ambient temperature was 20 ℃ and the humidity was 55%.
Dissolving 1g of copper sulfate in 50g of water, adjusting the pH value to 8, adding 1g of glucose, heating in a 75 ℃ water bath for 0.5 hour, synthesizing cuprous oxide in situ, washing the obtained photocatalytic fiber membrane with ethanol for 2 times, drying at 40 ℃, removing unreacted monomers and free particles, and obtaining the photocatalytic fiber membrane, wherein the SEM is shown in figure 1.
Subsequently, a photocatalysis experiment is carried out under a xenon lamp, and the yield of the carbon monoxide is measured to be 41.25 mu mol g-1h-1As shown in fig. 2, the photocatalytic performance of the fiber is greatly improved.
Example 2: 13g of thermoplastic polyurethane was dissolved in 87g of 99.9% N, N-dimethylformamide to give a spinning dope with a mass fraction of 13%. The dope system was loaded into a 20mL syringe fixed in a microflow pump. Set the flow rate of the micro flow pump to 5mLh-1. The voltage was set at 12kV and a polyamide 66 fiber film was obtained on the receiver. The ambient temperature was 25 ℃ and the humidity was 58%.
Dissolving 2g of tetrabutyl titanate in 50g of water, adjusting the pH value to 9, adding 1.5g of ferric chloride, heating in a water bath at 80 ℃ for 1.5 hours, synthesizing titanium dioxide in situ, washing the obtained photocatalytic fiber membrane with ethanol for 4 times, drying at 45 ℃, and removing unreacted monomers and free particles to obtain the photocatalytic fiber membrane.
Subsequently, a photocatalysis experiment is carried out under a xenon lamp, and the carbon monoxide yield is measured to be 43.66 mu mol g-1h-1Greatly improves the photocatalysis performance of the fiber.
Example 3: 15g of polycaprolactone was dissolved in 85g of 88% formic acid to form a spinning dope with a mass fraction of 15%. The dope system was loaded into a 20mL syringe fixed in a microflow pump. Setting the flow rate of the micro flow pump to 3mLh-1. With a voltage set at 15kV, the focus is obtained at the receiverAn acrylic fiber film. The ambient temperature was 27 ℃ and the humidity was 60%.
Dissolving 3g of pyrrole in 50g of water, adjusting the pH value to 11, adding 2g of ferric sulfate, heating in a water bath at 80 ℃ for 2 hours, synthesizing polypyrrole in situ, washing the obtained photocatalytic fiber membrane with ethanol for 6 times, drying at 50 ℃, and removing unreacted monomers and free particles to obtain the photocatalytic fiber membrane.
Subsequently, a photocatalysis experiment is carried out under a xenon lamp, and the yield of the carbon monoxide is measured to be 45.33 mu mol g-1h-1Greatly improves the photocatalysis performance of the fiber.
Example 4: 17g of polyacrylonitrile was dissolved in 83g of 99.9% N, N-dimethylformamide to form a spinning solution with a mass fraction of 17%. The dope system was loaded into a 20mL syringe fixed in a microflow pump. Set the flow rate of the micro flow pump to 7mLh-1. The voltage was set at 17kV and a polycaprolactone fiber film was obtained on the receiver. The ambient temperature was 30 ℃ and the humidity 63%.
Dissolving 4g of copper sulfate in 50g of water, adjusting the pH value to 12, adding 2.5g of ferric chloride, heating in a water bath at 85 ℃ for 2.5 hours, synthesizing cuprous oxide in situ, washing the obtained photocatalytic fiber membrane with ethanol for 8 times, drying at 55 ℃, and removing unreacted monomers and free particles to obtain the photocatalytic fiber membrane.
Subsequently, a photocatalysis experiment is carried out under a xenon lamp, and the carbon monoxide yield is measured to be 39.65 mu mol g-1h-1Greatly improves the photocatalysis performance of the fiber.
Example 5: 20g of polyimide was dissolved in 80g of 98% ethanol to form a spinning solution with a mass fraction of 20%. The dope system was loaded into a 20mL syringe fixed in a microflow pump. Setting the flow rate of the micro flow pump to 10mLh-1. The voltage was set at 20kV and a polyimide fiber membrane was obtained on the receiver. The ambient temperature was 35 ℃ and the humidity 65%.
Dissolving 5g of copper sulfate in 50g of water, adjusting the pH value to 14, adding 3g of glucose, heating in a water bath at 90 ℃ for 3 hours, synthesizing cuprous oxide in situ, washing the obtained photocatalytic fiber membrane with ethanol for 10 times, drying at 60 ℃, and removing unreacted monomers and free particles to obtain the photocatalytic fiber membrane.
Subsequently, a photocatalysis experiment is carried out under a xenon lamp, and the yield of the carbon monoxide is measured to be 41.25 mu mol g-1h-1Greatly improves the photocatalysis performance of the fiber.
Claims (7)
1. A method for preparing photocatalytic fibers by microfluid electrostatic spinning comprises the following specific steps:
(1) dissolving a polymer in a solvent, and fully dissolving to obtain a polymer spinning solution;
(2) adjusting the parameters of microfluid electrostatic spinning to carry out electrostatic spinning to prepare a uniform polymer fiber membrane;
(3) in-situ synthesis of the catalyst: mixing reactants and water in a reactor to form a solution, adjusting the pH value of the solution, then putting a polymer fiber membrane into the solution, putting the reactor into a reaction bath, dropwise adding an oxidant, and heating for in-situ growth; and then washing and drying to remove unreacted monomers and free particles to obtain the photocatalytic fiber.
2. The method of claim 1, wherein: in the step (1), the polymer is one or a combination of polyamide 66, thermoplastic polyurethane, polyacrylonitrile, polycaprolactone, polyimide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl chloride or polyvinylidene fluoride; the solvent is one or more of formic acid, ethanol or N, N-dimethylformamide; the mass fraction of the polymer spinning solution is 10-20%.
3. The method of claim 1, wherein: the parameters of the microfluid electrostatic spinning in the step (2) are as follows: the liquid inlet amount is 1-10mLh-1The voltage is 10-20kV, the environmental temperature is 20-35 ℃, and the environmental humidity is 55-65%.
4. The method of claim 1, wherein: the reactant in the step (3) is one of copper sulfate, tetrabutyl titanate or pyrrole and a derivative thereof; the mass ratio of reactants to water is (1-5): 50.
5. the method of claim 1, wherein: the oxidant is one or the combination of glucose, ferric chloride or ferric sulfate; the mass ratio of the oxidant to the water is (1-3): 50.
6. the method of claim 1, wherein: the PH value range in the step (3) is 8-14; the heating temperature of the reaction bath is 75-90 ℃, and the heating time is 0.5-3 hours.
7. The method of claim 1, wherein: the washing solvent in the step (3) is ethanol, and the washing times are 2-10 times; the drying temperature is 40-60 ℃.
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| CN105129835A (en) * | 2015-08-06 | 2015-12-09 | 上海应用技术学院 | Hexacosahedral cuprous oxide nanometer particle preparation method |
| CN105749914A (en) * | 2016-02-01 | 2016-07-13 | 郑州大学 | Symmetric difunctional photocatalyst, double-chamber photoreactor and method for photocatalytic reduction of carbon dioxide |
| CN106345314A (en) * | 2016-09-23 | 2017-01-25 | 江苏大学 | Porous ferric oxide-titanium oxide-activated carbon complex fiber membrane and preparation method |
| CN106673051A (en) * | 2017-01-22 | 2017-05-17 | 郑州轻工业学院 | Preparation method of cuprous oxide super crystal material |
| CN107398293A (en) * | 2017-08-06 | 2017-11-28 | 武汉轻工大学 | A kind of fibrous Z-type photochemical catalyst TiO for handling organic sewage2/g‑C3N4Preparation method |
| CN109331796A (en) * | 2018-11-20 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of magnetic fibre film loaded optic catalyst and preparation method for wastewater treatment |
| CN110947422A (en) * | 2019-12-09 | 2020-04-03 | 东华大学 | Preparation method of high-molecular gold nanoparticle composite fiber membrane capable of repeatedly utilizing catalytic performance |
| CN111167514A (en) * | 2020-02-17 | 2020-05-19 | 南京理工大学 | CdS/PAN fibrous composite photocatalyst based on in-situ growth and preparation method thereof |
| CN111514931A (en) * | 2020-04-21 | 2020-08-11 | 东华大学 | Preparation method of high polymer and palladium-gold nanorod fiber film with photocatalytic performance |
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