CN109999809B - Preparation method and application of iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead - Google Patents
Preparation method and application of iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead Download PDFInfo
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- 239000011324 bead Substances 0.000 title claims abstract description 45
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 45
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 44
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229960003638 dopamine Drugs 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
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- 238000005266 casting Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/39—
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- B01J35/58—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the technical field of material preparation and environmental pollution treatment, and provides a preparation method of iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads, which comprises the following steps: step 1, preparing an iron oxide @ biomass carbon fiber composite photo-Fenton catalyst; step 2, preparing pDA-PVDF powder; and 3, preparing the photo-Fenton composite beads based on a phase inversion technology and a dopamine self-polymerization technology. The invention utilizes pDA-PVDF beads as the carrier of the photo-Fenton catalyst, not only can fix the powder catalyst and be beneficial to practical application, but also can effectively inhibit the loss of iron ions and improve the stability of a catalytic system. The method has the advantages of simple synthesis, high degradation efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and environmental pollution treatment, and relates to a preparation method and application of iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads for efficiently degrading methyl orange.
Background
Azo dyes are dyes which contain one or more azo groups (-N ═ N-) and are linked to at least one aromatic structure. Azo dyes have the characteristics of various colors, simple process, low production cost and strong dyeing capability, so the azo dyes are widely applied to dyeing of textiles and coloring of products such as paper, leather, plastics and the like, and also have application in food and cosmetics. Although azo dyes are widely used, part of azo dyes can generate 24 carcinogenic aromatic amine compounds through reductive cleavage, and if the compounds are absorbed by human bodies, the compounds can seriously threaten the health of the human bodies. Especially in the products such as textile, clothes and leather, the dyes can enter human body through respiratory tract, esophagus and skin mucous membrane after contacting with human body for a long time, and cancerogenic aromatic amine can be reduced and decomposed under specific conditions along with metabolism in the human body. Therefore, the method has important significance in efficiently degrading the azo dye remained in the water body.
Advanced Oxidation Processes (AOPs) are characterized by the generation of hydroxyl radicals (OH) with a strong oxidizing action, capable of degrading these organic pollutants into small molecules with low or no toxicity. The heterogeneous photo-fenton process is a promising water treatment strategy that can replace homogeneous fenton reagents. However, there are two significant challenges during heterogeneous photo-fenton reactions: (i) the powdery photo-Fenton catalyst is difficult to recover and operate in practical application; (ii) the stability of the catalyst is poor due to severe loss of active metals during operation.
Disclosure of Invention
Aiming at the problems in the prior art, the polymer beads constructed by the simple phase inversion technology can easily and effectively fix the photo-Fenton catalyst, and meanwhile, the multistage pore structure in the beads can not hinder the diffusion of organic pollutants. In addition, polydopamine (pDA) is a multifunctional surface engineering coating that can be applied to the surface of almost any material without affecting the inherent structure of the polymer beads. Because the catechol groups are rich and have stronger metal ion coordination capacity, the pDA layer can inhibit the loss of iron ions. In addition, polydopamine can be used as a medium for promoting electron transfer, so that the photocatalysis performance of the photo-Fenton reaction is improved.
The invention dropwise adds the casting solution into the coagulating bath to prepare the photo-Fenton composite bead. The obtained beads have the diameter of about 3mm, and are easier to recycle and use compared with a split photo-Fenton catalyst and are positioned at the continuous part of an actual water sampleAnd (6) processing. In a photo-Fenton system, the polydopamine, the biological carbon and the elementary iron in the iron oxide can promote Fe3+/Fe2+Thereby improving the catalytic performance. In addition, the polydopamine modified PVDF plays a role of a 'barrier', can effectively inhibit the loss of iron examples, and improves the stability of the photo-Fenton composite beads. The invention provides a novel method which is generally applicable to the enlarged application of the photo-Fenton powder catalyst, and can realize the effective degradation of the actual environmental wastewater to a certain extent.
A preparation method of iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads comprises the following steps:
step 1, preparing iron oxide @ biomass carbon fibers:
cleaning and drying wild cattail wool, weighing a certain amount of cattail wool in a crucible, transferring the cattail wool to a tube furnace, calcining the cattail wool for a certain time at a certain temperature under a nitrogen atmosphere, and naturally cooling the cattail wool and taking out the cattail wool to obtain biomass Carbon Fiber (CF);
dispersing a certain amount of CF in water, and adding a certain amount of FeSO into the above dispersion4·7H2And O, oscillating for a certain time, drying, transferring the obtained solid to a tube furnace, calcining for a second time at a certain temperature in a nitrogen atmosphere for a certain time, naturally cooling, taking out to obtain iron oxide @ biomass Carbon fiber (Fe-based oxide @ Carbon fiber, FCF), and grinding into powder by using a mortar for later use.
proportionally dispersing Dopamine (DA) and polyvinylidene fluoride (PVDF) in a Tris-HCl buffer solution, adding a certain amount of ethanol, adjusting the pH value to 8.5, then stirring vigorously at room temperature, and finally filtering to obtain pDA-PVDF powder and drying;
mixing the FCF powder prepared in the step 1, the pDA-PVDF powder prepared in the step 2 and N-methylpyrrolidone (NMP) according to a ratio, then mechanically stirring at a certain temperature to obtain a bead casting liquid A, finally dropwise adding the bead casting liquid A into deionized water, replacing the deionized water for multiple times, ensuring that an NMP solvent is completely replaced into the water, and forming the FCF @ pDA-PVDF photo-Fenton composite beads for later use.
In the step 1, the calcination temperature of the cattail wool is 800-850 ℃, the calcination time is 3-5 h, and the temperature rise rate of a tubular furnace is 5 ℃/min; the CF and FeSO4·7H2The proportion of O is 0.3 g: 1-3 mmol; the oscillation time is 12 h; the second calcination temperature is 550-850 ℃, the calcination time is 3-5 h, and the heating rate is 5 ℃/min;
in the step 2, the mass ratio of DA to PVDF is 1: 10, the concentration of the dopamine in the Tris-HCl buffer solution is 2 mg/mL; the volume ratio of the Tris-HCl buffer solution to the ethanol is 30: 1; the violent stirring time is 6 hours; the rotating speed is 500-800 r/min;
in step 3, the mass ratio of FCF powder, pDA-PVDF powder and NMP in the bead casting solution A is 0.05-0.15 g: 2 g: 17.85-17.95 g; the mechanical stirring temperature is 50 ℃, and the stirring time is 4-6 h.
The NMP in the above technical scheme acts as a solvent to dissolve PVDF to prepare the bead casting solution a.
The PVDF described in the above-mentioned technical solution functions as a matrix.
The deionized water in the technical scheme is used as a non-solvent.
The iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead prepared by the method is used for photocatalytic degradation of methyl orange.
The invention has the beneficial effects that:
(1) the existence of simple substance iron and biological carbon can promote Fe3+/Fe2+The method can generate more hydroxyl free radicals, improve the photocatalysis efficiency and effectively degrade organic pollutants.
(2) The PVDF beads modified by pDA are used for fixing the photo-Fenton catalyst, and the obtained composite beads well solve the problem that the split photo-Fenton catalyst is difficult to be practically applied. In addition, the polydopamine can effectively inhibit the loss of iron ions, so that the stability of a catalytic system is effectively improved. The whole preparation method is simple and convenient, and provides new insight for the expanded application of the Fenton catalytic system.
Drawings
FIG. 1a is an XRD pattern of the prepared composite (where CF represents biomass carbon fiber, FCF represents iron oxide @ biomass carbon fiber, PB represents PVDF bead, DPB represents pDA-PVDF bead, FPB represents iron oxide @ biomass carbon fiber @ PVDF bead, FDPB represents iron oxide @ biomass carbon fiber @ pDA-PVDF bead), FIG. 1b is an actual photograph of the composite bead, and FIG. 1c is a cross-sectional scanning electron micrograph of the bead;
fig. 2a is a degradation efficiency curve of different materials under the condition of pH 3, and fig. 2b is a photocatalytic degradation efficiency curve of FDPB under different pH conditions.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
The present invention is exemplified by a total mass of the bead casting liquid of 20 g.
Example 1:
(1) preparation of FCF composite photo-Fenton catalyst
Weighing dried cattail wool in a crucible, transferring the crucible to a tube furnace, calcining the cattail wool for 3 hours at the temperature of 800 ℃, wherein the heating rate is 5 ℃/min, and taking out the cattail wool after natural cooling to obtain CF for later use; 0.3g of CF and 1mmol of FeSO were taken4·7H2Dispersing O in 35mL of deionized water, and oscillating for 12h at room temperature; and after drying, transferring the obtained solid to a tubular furnace, and calcining for 3 hours at 850 ℃ to obtain the FCF composite Fenton catalyst.
(2) Preparation of FCF @ pDA-PVDF photo-Fenton composite beads
Firstly, 0.6g of dopamine powder and 6g of PVDF powder are dispersed in 300mL of Tris-HCl buffer solution, then 10mL of ethanol is added, the pH value of the solution is adjusted to be 8.5, the mixed solution is vigorously stirred for 6 hours to complete the self-polymerization of polydopamine on the surface of the PVDF powder, and finally, the pDA-PVDF powder is obtained through filtering, washing and drying. 0.05g of FCF, 2g of pDA-PVDF powder and 17.95g of NMP solvent were weighed and mixed together, and stirred at 50 ℃ for 4 hours to obtain a bead casting solution. And then pumping the casting solution into a 10mL syringe, dropwise adding the casting solution into deionized water, and carrying out phase inversion to obtain the composite beads.
Example 2:
under the condition of ensuring that other conditions are unchanged, establishing a comparative test as follows: when preparing the FCF composite Fenton catalyst, 0.3g CF and 1mmol FeSO are taken4·7H2Dispersing O in 35mL of deionized water, and oscillating for 12h at room temperature; and after drying, transferring the obtained solid to a tubular furnace, and calcining for 3 hours after changing the calcining temperature to 550 ℃ to obtain the FCF composite photo-Fenton catalyst.
Example 3:
under the condition of ensuring that other conditions are unchanged, establishing a comparative test as follows: when preparing the FCF composite Fenton catalyst, CF and FeSO are changed4·7H2The load condition of the iron oxide is examined by taking 0.3g of CF and 3mmol of FeSO4·7H2Dispersing O in 35mL of deionized water, and oscillating for 12h at room temperature; and after drying, calcining for 3 hours at 850 ℃ to obtain the FCF composite photo-Fenton catalyst.
Example 4:
when photo-fenton composite beads were prepared (other conditions were not changed), the optimum amount of the fenton catalyst to be added and the influence of the amount to be added on the photocatalytic performance were examined by changing the amount of FCF to be added (0.1g, 0.15 g).
As can be seen in fig. 1, the composite material has characteristic peaks for various iron oxides and bio-made carbon fibers, demonstrating the successful synthesis of the composite material.
As can be seen from fig. 2a, the constructed FDPB almost completely decolorizes methyl orange within 60min, has good degradation efficiency, and is second only to powdered FCF; while other composites have lower degradation properties. As can be seen from fig. 2b, the constructed FDPB showed different degradation efficiencies under different pH conditions, wherein the degradation rate reached the highest at pH 1.7.
The degradation effect of the constructed composite Fenton beads on methyl orange reaches more than 99%, and good catalytic performance is kept after 6 cycles.
Claims (7)
1. A preparation method of the iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead is characterized by comprising the following steps:
step 1, preparing iron oxide @ biomass carbon fibers:
cleaning and drying wild cattail wool, weighing a certain amount of cattail wool in a crucible, transferring the crucible to a tubular furnace, calcining the cattail wool for a certain time at a certain temperature under a nitrogen atmosphere, and naturally cooling the cattail wool and taking out the cattail wool to obtain biomass carbon fiber CF;
dispersing a certain amount of CF in water, and adding a certain amount of FeSO4·7H2O, oscillating for a certain time, drying, transferring the obtained solid to a tube furnace, calcining for a certain time at a certain temperature under a nitrogen atmosphere, naturally cooling, taking out to obtain iron oxide @ biomass carbon fiber FCF, and grinding the iron oxide @ biomass carbon fiber FCF into powder by using a mortar for later use;
step 2, preparing pDA-PVDF powder;
dispersing dopamine DA and polyvinylidene fluoride PVDF in a Tris-HCl buffer solution according to a certain proportion, adding a certain amount of ethanol, then adjusting pH, then violently stirring at room temperature, finally filtering to obtain pDA-PVDF powder and drying;
step 3, preparing iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads;
mixing the FCF powder prepared in the step 1, the pDA-PVDF powder prepared in the step 2 and N-methylpyrrolidone NMP in proportion, then mechanically stirring at a certain temperature to obtain a bead casting liquid A, finally, dropwise adding the bead casting liquid A into deionized water, replacing the deionized water for multiple times, ensuring that an NMP solvent is completely replaced into the water, and forming the FCF @ pDA-PVDF photo-Fenton composite beads for later use.
2. The method for preparing the iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead as claimed in claim 1, wherein in the step 1, the cattail wool calcination temperature is 800-850 ℃, the calcination time is 3-5 h, and the temperature rise rate of the tube furnace is 5 ℃/min.
3. Iron according to claim 1The preparation method of the oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead is characterized in that in step 1, CF and FeSO are adopted4·7H2The proportion of O is 0.3 g: 1-3 mmol; the oscillation time is 12 h; the second calcination temperature is 550-850 ℃, the calcination time is 3-5 h, and the heating rate is 5 ℃/min.
4. The method of claim 1, wherein in step 2, the mass ratio of DA to PVDF is 1: 10, the concentration of the dopamine in the Tris-HCl buffer solution is 2 mg/mL; the volume ratio of the Tris-HCl buffer solution to the ethanol is 30: 1; the pH was 8.5.
5. The method of making the iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads of claim 1, wherein in step 2, the vigorous stirring time is 6 hours; the rotation speed is 500-800 r/min.
6. The method for preparing the iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite beads according to claim 1, wherein in the step 3, the mass ratio of the FCF powder, the pDA-PVDF powder and the NMP in the bead casting solution A is 0.05-0.15 g: 2 g: 17.85-17.95 g; the mechanical stirring temperature is 50 ℃, and the stirring time is 4-6 h.
7. Use of the iron oxide @ biomass carbon fiber @ pDA-PVDF photo-Fenton composite bead prepared by the preparation method of any one of claims 1 to 6 for photocatalytic degradation of methyl orange.
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