CN115569673A - Nanofiber membrane with organic dye photocatalytic degradation function and preparation method thereof - Google Patents

Nanofiber membrane with organic dye photocatalytic degradation function and preparation method thereof Download PDF

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CN115569673A
CN115569673A CN202211279942.9A CN202211279942A CN115569673A CN 115569673 A CN115569673 A CN 115569673A CN 202211279942 A CN202211279942 A CN 202211279942A CN 115569673 A CN115569673 A CN 115569673A
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nanofiber membrane
function
photocatalytic degradation
photocatalytic
membrane
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陈雪飞
马雪
张倩倩
王逸
潘天帝
杨晓华
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Zhejiang Sci Tech University ZSTU
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Zhejiang Sci Tech University ZSTU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30Halides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58Fabrics or filaments
    • B01J35/59Membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0205Impregnation in several steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0234Impregnation and coating simultaneously
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses a nanofiber membrane with the function of photocatalytic degradation of organic dye and a preparation method thereof, and the preparation method of the nanofiber membrane with the function of photocatalytic degradation of organic dye comprises the following steps of a) immobilization: sequentially dipping the nanofiber membrane into a tannic acid solution and an iron chloride hexahydrate solution, and repeating for a plurality of times to obtain a blank membrane; b) And (3) post-treatment: drying the blank film prepared in the step a) to obtain a finished product. According to the invention, the metal polyphenol coating with the photocatalytic function is formed on the surface of the nanofiber membrane by a layer-by-layer self-assembly method, the overall preparation process is simple, the cost is low, the environment is protected, and the prepared nanofiber membrane has a high specific surface area, is beneficial to improving the photocatalytic performance, and is very suitable for photocatalytic degradation of organic dyes in printing and dyeing wastewater.

Description

Nanofiber membrane with organic dye photocatalytic degradation function and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of photocatalytic printing and dyeing wastewater treatment, in particular to a nanofiber membrane with a function of photocatalytic degradation of organic dye and a preparation method thereof.
[ background of the invention ]
In the production process of the textile industry, printing and dyeing processing is an indispensable step as a key means for improving the added value of textiles. However, the printing and dyeing process inevitably produces printing and dyeing wastewater, such as rhodamine B dye which is carcinogenic and mutagenic, and the wastewater containing the rhodamine B dye has deep chroma, high organic pollutant content and poor biodegradability, thereby seriously harming the water body environment and the human health.
At present, the treatment method of the printing and dyeing wastewater mainly comprises a photocatalysis method, a physical method, a biological method and the like. The photocatalysis method can utilize light energy to drive materials to carry out catalytic reaction, thereby degrading, decoloring and mineralizing organic pollutants harmful to human bodies and environment into inorganic micromolecular substances. The photocatalytic method has been rapidly developed in recent years because of its advantages of relatively thorough degradation of organic pollutants and utilization of solar energy. At present, photocatalysts mainly comprise metal oxides, metal-organic frameworks and inorganic semiconductors, such as TiO 2 、WO 3 、SnO 2 And CdS, etc. However, the photocatalytic material generally has the defects of high price, complex preparation, difficult guarantee of high specific surface area, low sunlight utilization rate and the like, so that the application of the photocatalytic material in printing and dyeing wastewater is limited. In addition, if the photocatalytic material is directly put into water and dispersed for use, it is difficult to recover and the loss is large, such as a photocatalyst disclosed in (publication) No. CN106865685BA treatment method for degrading rhodamine B dye wastewater; if the photocatalytic material is used as a coating, a large amount of effective active surface of the photocatalytic material is lost, so that the using amount is increased, and the cost is increased, for example, a method for preparing a photocatalytic film for dye degradation with the publication (publication) number of CN108927225A is disclosed.
[ summary of the invention ]
The invention aims to solve the problems in the prior art, and provides a nanofiber membrane with a photocatalytic organic dye degradation function and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the nanofiber membrane with the function of photocatalytic degradation of organic dye comprises the following steps:
a) Solid loading: sequentially dipping the nanofiber membrane in a tannic acid solution and a ferric chloride hexahydrate solution, and repeating for a plurality of times to obtain a blank membrane;
b) And (3) post-treatment: drying the blank film prepared in the step a) to obtain a finished product.
Preferably, in the step a), the nanofiber membrane is a polyacrylonitrile nanofiber membrane.
Furthermore, the polyacrylonitrile nanofiber membrane is prepared from an N, N-dimethylformamide solution of polyacrylonitrile by an electrostatic spinning technology, wherein the concentration of the N, N-dimethylformamide solution of the polyacrylonitrile is 5-15%.
Preferably, in the step a), the concentration of the tannic acid solution is 0.1 to 5mg/mL.
Preferably, in the step a), the concentration of the ferric chloride hexahydrate solution is 0.1-5 mg/mL.
Preferably, in the step a), the time for each immersion is 1 to 20min.
Preferably, the cycle is repeated 1 to 20 times in the step a).
The nanofiber membrane with the function of photocatalytic degradation of organic dye is prepared by the preparation method.
The invention has the beneficial effects that:
1) The metal polyphenol coating with the photocatalytic function is prepared on the surface of the nanofiber membrane by adopting a layer-by-layer self-assembly method, and the metal polyphenol coating is fixedly loaded on the nanofiber membrane, so that the problem of difficulty in recovering a photocatalyst is well solved, organic pollutants enriched in water can be intercepted in time by utilizing the membrane effect and degraded in situ under the photocatalytic effect, and the nanofiber membrane has a large specific surface, so that the photocatalytic efficiency can be effectively improved, and the contact area of the organic pollutants and the photocatalyst can be increased;
2) The metal polyphenol coating is firmly combined on the surface of the nanofiber membrane by utilizing hydrogen bonds, pi-pi stacking and hydrophobic interaction, so that the metal polyphenol coating is not easy to fall off;
3) The integral preparation process is simple, low in cost, green and environment-friendly, is convenient for large-scale production, and is very suitable for photocatalytic degradation of organic dyes in printing and dyeing wastewater.
The features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
[ description of the drawings ]
FIG. 1 is an electron microscope image of a finished nanofiber membrane with photocatalytic degradation organic dye function prepared in the first embodiment after being magnified 1000;
FIG. 2 is an electron microscope image of the finished nanofiber membrane with the function of photocatalytic degradation of organic dye prepared in the first embodiment after being enlarged by 10000;
FIG. 3 is a graph showing the change of the photocatalytic efficiency of the nanofiber membrane finished product with the function of photocatalytic degradation of organic dye according to the embodiment I and the embodiment II along with the photocatalytic time;
fig. 4 is an absorption spectrum of the nanofiber membrane finished product with the function of photocatalytic degradation of organic dyes prepared in the first and second examples.
[ detailed description ] A
The first embodiment is as follows:
firstly, dissolving polyacrylonitrile with the concentration of 10% in N, N-dimethylformamide, stirring for 4 hours at 60 ℃ by using a magnetic stirrer, and carrying out ultrasonic treatment to form a uniform spinning precursor solution. And then, moving the spinning precursor solution into an injector of an electrostatic spinning machine, simultaneously adopting a flat plate coated with aluminum foil and tinfoil as a receiving device, and starting electrostatic spinning (when the spinning precursor solution is sprayed out and the solvent is evaporated, the polyacrylonitrile nanofiber membrane can be obtained). In the electrostatic spinning process, the needle model is 22G; the electrostatic voltage is 10KV; the flow rate of the spinning solution is 0.5mL h -1 (ii) a The distance between the tip of the needle and the receiving means is 10cm. Then, the nanofiber membrane was immersed in a tannic acid solution of 3mg/mL for 10min, and then immersed in an iron chloride hexahydrate solution of 0.75mg/mL for 10min, and the cycle was repeated 1 time to obtain a green membrane. And finally, drying the blank film to obtain a nanofiber film finished product with the function of photocatalytic degradation of organic dye. In addition, the electron microscope images of 1000 times and 10000 times of amplification of the nanofiber membrane finished product with the function of photocatalytic degradation of organic dye can be seen in fig. 1 and fig. 2 respectively.
Example two:
firstly, dissolving polyacrylonitrile with the concentration of 10% in N, N-dimethylformamide, stirring for 4 hours at the temperature of 60 ℃ by using a magnetic stirrer, and carrying out ultrasonic treatment to form uniform spinning precursor solution. And then, moving the spinning precursor solution into an injector of an electrostatic spinning machine, simultaneously adopting a flat plate coated with aluminum foil and tinfoil as a receiving device, and starting electrostatic spinning (when the spinning precursor solution is sprayed out and the solvent is evaporated, the polyacrylonitrile nanofiber membrane can be obtained). In the electrostatic spinning process, the needle head is 22G in model; electrostatic voltage 10KV; the flow rate of the spinning solution is 0.5mL h -1 (ii) a The distance between the tip of the needle and the receiving means is 10cm. Then, the nanofiber membrane is firstly soaked in 3mg/mL tannic acid solution for 10min, then is soaked in 0.75mol/mL ferric chloride hexahydrate solution for 10min, and the cycle is repeated for 5 times to obtain a blank membrane. And finally, drying the blank film to obtain a nanofiber film finished product with the function of photocatalytic degradation of organic dye.
Example three:
and (3) carrying out a photocatalytic performance test on the nanofiber membrane finished product with the function of photocatalytic degradation of the organic dye prepared in the first and second embodiments. Wherein, the organic wastewater adopted in the test is 20mL of 10mg/L rhodamine B solution; the reaction condition is 300W xenon lamp; controlling the reaction temperature to be 25 ℃; the reaction time is 8h; the distance between the lamp tube and the rhodamine B solution is 12cm.
Referring to fig. 3 and 4, experimental results prove that the photocatalytic efficiency of the nanofiber membrane finished product with the function of photocatalytic degradation of organic dyes prepared in the first and second embodiments can reach 93%.
The above embodiments are illustrative of the present invention, and are not intended to limit the present invention, and any simple modifications of the present invention are within the scope of the present invention.

Claims (8)

1. The preparation method of the nanofiber membrane with the function of photocatalytic degradation of organic dye is characterized by comprising the following steps:
a) Solid loading: sequentially dipping the nanofiber membrane in a tannic acid solution and a ferric chloride hexahydrate solution, and repeating for a plurality of times to obtain a blank membrane;
b) And (3) post-treatment: drying the blank film prepared in the step a) to obtain a finished product.
2. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes according to claim 1, wherein the method comprises the following steps: in the step a), the nanofiber membrane is a polyacrylonitrile nanofiber membrane.
3. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes according to claim 2, wherein the method comprises the following steps: the polyacrylonitrile nanofiber membrane is prepared from an N, N-dimethylformamide solution of polyacrylonitrile through an electrostatic spinning technology, wherein the concentration of the N, N-dimethylformamide solution of the polyacrylonitrile is 5-15%.
4. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes as claimed in claim 1, wherein the method comprises the following steps: in the step a), the concentration of the tannic acid solution is 0.1-5 mg/mL.
5. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes as claimed in claim 1, wherein the method comprises the following steps: in the step a), the concentration of the ferric chloride hexahydrate solution is 0.1-5 mg/mL.
6. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes according to claim 1, wherein the method comprises the following steps: in the step a), the time for each dipping is 1-20 min.
7. The method for preparing the nanofiber membrane having the function of photocatalytic degradation of organic dyes according to claim 1, wherein the method comprises the following steps: in the step a), the circulation is repeated for 1 to 20 times.
8. A nanofiber membrane with a function of degrading organic dyes through photocatalysis, which is prepared by the preparation method of any one of claims 1 to 7.
CN202211279942.9A 2022-10-19 2022-10-19 Nanofiber membrane with organic dye photocatalytic degradation function and preparation method thereof Pending CN115569673A (en)

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Publication number Priority date Publication date Assignee Title
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CN105214524A (en) * 2015-10-16 2016-01-06 南京大学 Tunica fibrosa of adsorbable heavy-metal ion removal and photocatalysis degradation organic contaminant and preparation method thereof
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CN111203107A (en) * 2020-02-19 2020-05-29 东华大学 Polyphenol-iron nano film and preparation method and application thereof
CN111330463A (en) * 2020-03-04 2020-06-26 中国科学院过程工程研究所 Catalytic membrane and preparation method and application thereof
CN114042387A (en) * 2022-01-10 2022-02-15 中国科学院宁波材料技术与工程研究所 Photocatalytic degradation dye wastewater separation multilayer composite membrane and preparation method and application thereof

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