CN110075879B - Carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material and preparation method and application thereof - Google Patents
Carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- CN110075879B CN110075879B CN201910462008.2A CN201910462008A CN110075879B CN 110075879 B CN110075879 B CN 110075879B CN 201910462008 A CN201910462008 A CN 201910462008A CN 110075879 B CN110075879 B CN 110075879B
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000000463 material Substances 0.000 title claims abstract description 133
- 239000004005 microsphere Substances 0.000 title claims abstract description 111
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- 239000002131 composite material Substances 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 93
- BJINYZHIGSHXEP-UHFFFAOYSA-N bismuth;iodo hypoiodite Chemical class [Bi].IOI BJINYZHIGSHXEP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 34
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- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 241000235058 Komagataella pastoris Species 0.000 claims abstract description 6
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 45
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- 239000000243 solution Substances 0.000 claims description 29
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- 229910052797 bismuth Inorganic materials 0.000 claims description 8
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 8
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- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 claims description 2
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 claims description 2
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 abstract description 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/51—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material and a preparation method and application thereof. The preparation method of the composite photocatalytic material comprises the steps of preparing carbon-coated ferroferric oxide magnetic microspheres by a hydrothermal carbonization method, and loading the carbon-coated ferroferric oxide magnetic microspheres on the surface of bismuth oxyiodide in a hydrothermal codeposition mode. The pichia pastoris in the composite material is cheap and easy to obtain, is non-toxic and harmless, has simple and convenient preparation process, is green and environment-friendly, has easily controlled reaction conditions, and does not produce secondary pollution. The prepared composite catalytic material has the advantages of uniform particle size, high light absorption intensity, wide absorption range, high photo-generated carrier generation rate, good conduction effect, low recombination rate, high stability of the composite photocatalytic material, certain magnetism, capability of being recycled under the condition of an external magnetic field and environmental protection benefit. When the composite photocatalytic material is applied to photocatalytic degradation of antibiotic wastewater, the composite photocatalytic material has the advantages of fast degradation, high removal rate, convenience in operation, low cost, no secondary pollution and the like.
Description
Technical Field
The invention belongs to the field of material preparation and environmental water treatment, and particularly relates to a carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material as well as a preparation method and application thereof.
Background
The semiconductor photocatalytic oxidation technology is a modern water treatment technologyThe efficient degradation of organic pollutants, the low-toxicity conversion of heavy metals, the effective catalytic reduction of carbon dioxide, the hydrogen and oxygen production by water electrolysis and other reaction processes are realized by effectively converting solar energy and other light energy into chemical energy, and the method has wide environmental application prospect. But the conventional semiconductor material TiO2The forbidden band width is large (3.2eV), and the catalytic activity response can be only made to the ultraviolet spectrum which only accounts for 4% of the sunlight, so that the high-efficiency utilization of solar energy is limited. Thus, the development was responsive to visible light (460 nm)<λ<760nm) and its application in degrading common organic pollutants in industry becomes one of the development trends in the field of catalytic research.
In recent years, a trivalent bismuth oxyhalide compound BiOX (X ═ F, Cl, Br, I) has been widely noticed and studied for its high photocatalytic activity based on the development and application of materials responding to visible light catalysis. This is mainly due to the presence of [ Bi ] in the bismuth oxyhalide compound2O2]2+The layered crystal structure formed by interleaving the flat plate and the halogen ion layer can form a self-built internal electrostatic field, thereby promoting the generation and migration of photo-generated electrons and photo-generated holes and achieving higher solar spectrum utilization rate. Wherein Bi of bismuth oxyiodide (BiOI)3+Has a Bi 6s orbital crystal structure, can form a new valence electron band by hybridization with an O2 p orbital, and therefore has the narrowest band gap (1.8 eV) in the bismuth oxyhalide compound. The BiOI can be prepared by a hydrothermal synthesis method, a solvothermal method, an electrodeposition method, a decomposition method and the like, but the valence state change range of I in a single BiOI compound is very small, so that the adjustable range of the BiOI compound is limited, the defects of high charge carrier recombination rate, low conductivity, low active sites and the like of the BiOI are caused, and the application of the BiOI compound in the field of actual photocatalysis is limited. Magnetic and non-toxic Fe3O4The polymer has great specific surface area, good biocompatibility, conductivity and other excellent performances, so that the polymer is concerned and applied in the adsorption/catalysis field. But at the same time, Fe3O4The high charge recombination rate and the agglomeration property also limit the practical application of the single compound.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material. According to the method, a hydrothermal carbonization method is firstly utilized to prepare carbon-coated ferroferric oxide magnetic microspheres, and then the carbon-coated ferroferric oxide magnetic microspheres are loaded on the surface of bismuth oxyiodide in a hydrothermal codeposition mode.
The invention also aims to provide the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material prepared by the method. The material has high light absorption intensity, more active sites, high photo-generated charge conversion rate, certain magnetism and strong photocatalysis.
The invention further aims to provide application of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material, in particular application of degrading antibiotics in a low-energy visible LED light catalytic system.
The purpose of the invention is realized by the following technical scheme:
carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BiOI @ Fe)3O4@ C), comprising the following steps:
(1) adding yeast into the ferroferric oxide precursor solution, uniformly mixing, and performing hydrothermal carbonization for 12-14 h at 180-240 ℃ to obtain carbon-coated ferroferric oxide magnetic microspheres;
(2) mixing carbon-coated ferroferric oxide magnetic microspheres and bismuth nitrate pentahydrate according to the molar ratio of iron to bismuth of 1: (1-8) adding the mixture into an alcohol solvent, uniformly mixing, adding potassium iodide, heating for reaction, naturally cooling, continuing to react, washing and drying to obtain BiOI @ Fe3O4@ C composite photocatalytic material.
The yeast in the step (1) is preferably Pichia pastoris (Pichia pastoris GS115), which is purchased from China center for Industrial culture Collection of microorganisms with the accession number of CICC 1958.
The yeast in the step (1) is preferably added into the ferroferric oxide precursor solution in the form of yeast freeze-dried powder, and the mass ratio of the yeast freeze-dried powder to the ferroferric oxide precursor in the ferroferric oxide precursor solution is preferably (1)0.2-0.5): 2.5; more preferably (0.2 to 0.3): 2.5, wherein the ferroferric oxide precursor is FeCl3·6H2O。
The yeast freeze-dried powder is prepared by the following method: culturing the yeast on the culture solution, then centrifugally collecting, and drying at-50 ℃ for 24-36 h to prepare yeast freeze-dried powder.
The culture solution is preferably yeast extract peptone glucose culture solution (YPD, no agar); the culture time is preferably 36-48 h.
The ferroferric oxide precursor solution in the step (1) is preferably FeCl3·6H2O, anhydrous sodium acetate and sodium acrylate according to a mass ratio of 2.5: 3.4: 3.4 mixing the resulting mixed solution. .
FeCl in the mixed solution3·6H2The concentration of O is preferably 55.5 to 62.5 g/L.
The solvent of the ferroferric oxide precursor solution in the step (1) is preferably a mixed solvent of ethylene glycol and diethylene glycol with the volume ratio of 1: 1.
The mixing in the step (1) is preferably ultrasonic mixing, and the ultrasonic mixing time is preferably 60-90 min.
And (2) after hydrothermal carbonization in the step (1), washing with water, and drying at 60 ℃ for 12h to obtain the carbon-coated ferroferric oxide magnetic microspheres.
The molar ratio of iron to bismuth in the step (2) is preferably 1 (1-4).
The alcohol solvent in the step (2) is preferably ethylene glycol.
The concentration of the bismuth nitrate pentahydrate in the alcohol solvent in the step (2) is preferably 25-48.5 g/L.
The mixing condition in the step (2) is preferably oscillation reaction at 25-35 ℃ and 150-180 rpm for 30-60 min.
The molar ratio of the bismuth nitrate pentahydrate to the potassium iodide in the step (2) is preferably 1: 1.
The potassium iodide in the step (2) is preferably added in the form of a potassium iodide aqueous solution, and the concentration of the potassium iodide aqueous solution is 33-49.5 g/L.
The heating reaction in the step (2) is preferably carried out at the temperature of 80 ℃ for 3 hours.
And (3) carrying out the heating reaction in the step (2) under the oscillation condition.
And (3) the time for naturally cooling and continuously reacting in the step (2) is preferably 5-8 h, and the reaction is carried out under the oscillation condition.
The washing in the step (2) is preferably carried out by respectively washing with ethanol and water, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 12-14 h.
The carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material prepared by the method.
The carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material consists of a ferroferric oxide magnetic microsphere with an inner core and carbon with an outer shell, and is loaded around bismuth oxyiodide.
The application of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material in the field of photocatalytic degradation.
The application is preferably an application in the treatment of antibiotic wastewater.
The application of the method in treating antibiotic wastewater comprises the following steps: adding BiOI @ Fe3O4The @ C composite material is mixed with the antibiotic wastewater, the mixture is oscillated for a certain time under the condition of keeping out of the sun to achieve adsorption balance, and then photocatalytic degradation is carried out under the condition of visible light to complete the degradation treatment of the antibiotic wastewater.
The BiOI @ Fe3O4The dosage of the @ C composite material in the antibiotic wastewater is preferably 0.6-1 g/L.
The antibiotic in the antibiotic wastewater is preferably at least one of tetracycline, ciprofloxacin and amoxicillin.
The concentration of the antibiotic wastewater is preferably 10-30 mg/L.
The oscillation time is preferably 0-60 min.
The photocatalytic degradation is preferably carried out under the illumination condition of a low-energy-consumption LED lamp with the power of 5W.
The photocatalytic degradation is preferably carried out at the pH of the antibiotic wastewater itself (wherein tetracycline naturally has a pH of about 5.76 and tetracycline naturally has a pH of about 6.78).
The time of the photocatalytic degradation is preferably 10-120 min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a carbon-coated ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material, which contains yeast carbon-coated ferroferric oxide magnetic microspheres and a bismuth oxyiodide material; the yeast carbon-coated ferroferric oxide magnetic microsphere material takes ferroferric oxide magnetic microspheres as an inner core and takes yeast carbon as an outer shell and is loaded around bismuth oxyiodide. The ferroferric oxide has high conductivity and large specific surface area, is beneficial to transfer of photon-generated carriers, mass transfer diffusion of pollutants on the surface of the ferroferric oxide and contact with free radicals, the yeast carbon can promote the separation and conversion of the photon-generated carriers, and the ferroferric oxide with the surface coated with the yeast carbon has higher light excitation characteristic and higher charge carrier conversion efficiency. The bismuth oxyiodide has a small band gap and a visible light photoresponse characteristic, and on the basis, the yeast carbon-coated ferroferric oxide magnetic microsphere material is loaded around the BiOI, so that the yeast carbon, the ferroferric oxide and the bismuth oxyiodide are tightly combined together, the waste yeast can be effectively utilized, the agglomeration of the ferroferric oxide nano microspheres can be inhibited, the light absorption range of the BiOI can be enhanced, the light absorption strength of the BiOI can be increased, the compounding of a photon-generated carrier can be inhibited, and the photocatalytic performance and the corrosion resistance of the final composite photocatalytic material can be improved. The carbon-coated ferroferric oxide modified bismuth oxyiodide composite photocatalytic material has the characteristics of high visible light absorption intensity, wide absorption spectrum range, high photo-generated carrier yield, low recombination rate, strong stability and good photocatalytic performance, has certain magnetism, and is beneficial to cyclic utilization.
2. According to the invention, waste microbial biomass yeast is effectively utilized and is fired into a carbon layer coated on the surface of magnetite microspheres, and the BiOI @ Fe synthesized finally3O4@ C in Fe3O4@ C supported on the surface of BiOI and tightly bonded together, where Fe3O4@ C is a microspheroidal particle with a diameter of about 100-300 nm, and BiOI isRegular spherical shape with a diameter of about 2 μm; the ternary composite structure can effectively improve the specific surface area of the composite photocatalytic material and promote the transfer efficiency of photo-generated charges.
3. In the preparation process of the composite photocatalytic material, the hydrothermal carbonization method and the in-situ hydrothermal method are adopted to prepare the composite photocatalytic material, the reaction conditions are easy to regulate and control, the operation is simple and convenient, no secondary pollution is generated in the preparation process, and the preparation method has the advantages of environmental friendliness and the like.
4. The carbon-coated ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material prepared by the invention can generate photoproduction holes and photoproduction electrons under the visible light illumination condition of a low-energy-consumption LED lamp, and high-efficiency transfer is generated, so that the recombination rate is reduced, typical environmental pollution antibiotic wastewater is effectively treated, and the carbon-coated ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material has the characteristics of simplicity and convenience in operation, low cost, excellent photocatalytic degradation performance, rapidness in treatment and the like; the maximum degradation efficiency of the tetracycline is 90.6%, the maximum degradation efficiency of the ciprofloxacin is 71.1%, the degradation efficiency of the tetracycline under the same condition can still reach 78.1% after four times of cyclic utilization, and good stability and corrosion resistance are shown. Thus, the BiOI @ Fe of the present invention3O4The @ C composite semiconductor material can be widely applied to elimination and harmless treatment of antibiotic pollution, has important significance for developing carbon-modified catalytic materials of microorganisms, developing halogen photocatalysts and applying the carbon-modified catalytic materials to the environmental field, and also has important significance for high-valued application of yeast microorganisms and development of bismuth-based photocatalytic materials.
Drawings
FIG. 1 shows a yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) and a yeast carbon-coated ferroferric oxide magnetic microsphere (FC3) prepared in example 1 of the present invention, pure bismuth oxyiodide (BiOI) prepared in comparative example 1, and pure ferroferric oxide magnetic microsphere (Fe) prepared in comparative example 23O4) X-ray diffraction pattern of (a).
Fig. 2 is a scanning electron microscope image of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, wherein the magnification is 10000 times.
Fig. 3 is a transmission electron microscope image of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, wherein the magnification is 10000 times.
Fig. 4 is an ultraviolet-visible light diffuse reflection absorption spectrum of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, the pure bismuth oxyiodide (bio) material prepared in comparative example 1, and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2.
Fig. 5 is a photo-generated surface photo-electro-optical diagram of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, the pure bismuth oxyiodide (bio) material prepared in comparative example 1, and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2.
Fig. 6 is an impedance comparison graph of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, the pure bismuth oxyiodide (bio) material prepared in comparative example 1, and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2.
FIG. 7 is a comparison graph of the degradation effects of pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF1, BF2, BF4 and BF8) prepared in comparative example 2 and pure BiOI prepared in comparative example 1 on tetracycline under the irradiation of visible light (lambda >420nm) of an LED lamp.
FIG. 8 is a comparison graph of the degradation effect of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C2, BF2C3, BF2C4 and BF2C5) prepared in example 1 of the present invention and BF2 prepared in comparative example 2 on tetracycline degradation under the illumination of visible light (λ >420nm) of an LED lamp.
FIG. 9 is a comparison graph of degradation effects of yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, pure bismuth oxyiodide (BiOI) material prepared in comparative example 1, and pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2 on antibiotic ciprofloxacin under irradiation of visible light (λ >420nm) of an LED lamp.
Fig. 10 is a graph of the degradation effect of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention on cyclic degradation of tetracycline.
FIG. 11 shows a composite photocatalytic bismuth oxyiodide material modified with yeast carbon-coated ferroferric oxide magnetic microspheres (BF2C3), yeast carbon-coated ferroferric oxide magnetic microspheres (FC3) in example 1 of the present invention, and pure ferroferric oxide magnetic microspheres (Fe) prepared in comparative example 23O4) Magnetic hysteresis loop diagram of (1).
Detailed Description
The invention is described in further detail below with reference to specific examples and the accompanying drawings of the specification, without thereby limiting the embodiments of the invention.
The Pichia pastoris GS115 used in the embodiment of the invention is purchased from China center for Industrial culture Collection of microorganisms with a accession number of CICC 1958.
Example 1:
a yeast carbon-coated ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material is prepared by the following method:
(1) culturing pichia pastoris in YPD (agar-free) culture solution for 48h, taking out and centrifuging, washing with deionized water for 2-3 times, centrifuging, then putting into a freeze dryer, drying at-50 ℃ for 12h, and preparing into freeze-dried powder.
(2) 0.2g, 0.3g, 0.4g and 0.5g of the Pichia pastoris freeze-dried powder cultured in the step (1) and ferric chloride hexahydrate (FeCl) are respectively taken3·6H2O), anhydrous sodium acetate and sodium acrylate were dissolved together in 40mL of a mixed solvent of ethylene glycol and diethylene glycol (both solvents were 20mL in volume) to give a mixed suspension in which FeCl was present3·6H2The adding concentrations of O, anhydrous sodium acetate and sodium acrylate are respectively 62.5g/L, 85g/L and 85 g/L. Subjecting the mixed suspension to ultrasonic treatment at room temperatureTransferring to a polytetrafluoroethylene device after 1h, placing in a high-pressure reaction kettle for hydrothermal carbonization at 200 ℃ for 12h, cleaning with ultrapure water, and drying at 60 ℃ for 12h to obtain black yeast carbon-coated ferroferric oxide nano microspheres (Fe)3O4@ C), adding 0.2g, 0.3g, 0.4g and 0.5g of Pichia pastoris freeze-dried powder in sequence to obtain Fe3O4@ C is denoted FC2, FC3, FC4, and FC5 in that order.
(3) 0.0193g, 0.0386g, 0.0772g, 0.1544g of FC3 prepared in step (2) and 0.97g of bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) are mixed and added into 20mL of ethylene glycol, 10mL of potassium iodide (KI) ultrapure water solution (containing 0.33g of KI) is added into the solution drop by drop, and the solution is cooled and reacted for 5 hours at room temperature after shaking reaction at 80 ℃ for 3 hours. Collecting by external magnetic field acting force, washing with ethanol and ultrapure water for 2 times respectively, and drying at 60 deg.C for 12h to obtain carbon-coated ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material (BiOI @ Fe)3O4@ C) in the order of 0.0193g, 0.0386g, 0.0772g, 0.1544g of FC3, the BiOI @ Fe obtained was prepared3O4@ C is noted in order as BF8C3, BF4C3, BF2C3 and BF1C 3.
Comparative example 1:
preparation of pure bismuth oxyiodide (BiOI), comprising the steps of:
0.97g of bismuth nitrate pentahydrate (Bi (NO))3)3·5H2O) is dissolved in 20mL of ethylene glycol, 10mL of an ultra-pure aqueous solution of potassium iodide (KI) (containing 0.33g of KI) is added dropwise to the solution, the reaction is carried out at 80 ℃ for 3 hours with shaking, then the temperature is reduced, and the reaction is carried out at room temperature for 5 hours with shaking. After centrifugal collection, the mixture is washed by ethanol and ultrapure water for 2 times respectively and then dried for 12 hours at the temperature of 60 ℃. Thus obtaining the pure bismuth oxyiodide material (BiOI).
Comparative example 2:
pure ferroferric oxide microsphere modified bismuth oxyiodide composite photocatalytic material (BiOI @ Fe)3O4) The preparation method comprises the following steps:
(1) pure ferroferric oxide magnetic microsphere (Fe)3O4) The preparation of (1): FeCl is added3·6H2O, anhydrous sodium acetate and sodium acrylate togetherDissolving in 40mL of mixed solvent of ethylene glycol and diethylene glycol (the volume of both solvents is 20mL) to obtain mixed suspension, wherein FeCl is added3·6H2The adding concentrations of O, anhydrous sodium acetate and sodium acrylate are respectively 62.5g/L, 85g/L and 85 g/L. Ultrasonically treating the mixed suspension for 1h at room temperature, transferring the mixed suspension into a polytetrafluoroethylene device, placing the polytetrafluoroethylene device into a high-pressure reaction kettle for hydrothermal reaction at 200 ℃ for 12h, cleaning the mixed suspension with ultrapure water, and drying the cleaned mixed suspension for 12h at 60 ℃ to obtain the pure ferroferric oxide nano-microspheres (Fe)3O4)。
(2) Pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BiOI @ Fe)3O4) The preparation of (1): 0.0193g, 0.0386g, 0.0772g and 0.1544g of Fe prepared in the step (1) were respectively taken3O4With 0.97g Bi (NO)3)3·5H2O is mixed and added into 20mL of ethylene glycol, 10mL of potassium iodide (KI) ultrapure water solution (containing 0.33g of KI) is added into the solution drop by drop, and the solution is cooled after shaking reaction for 3h at 80 ℃ and then is shaken for 5h at room temperature. Collecting by external magnetic field acting force, washing with ethanol and ultrapure water for 2 times respectively, and drying at 60 deg.C for 12h to obtain pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide (BiOI @ Fe)3O4) Composite photocatalytic material, according to Fe3O4The obtained BiOI @ Fe was added in the amounts of 0.0193g, 0.0386g, 0.0772g and 0.1544g in this order3O4Noted in order as BF8, BF4, BF2 and BF 1.
The yeast carbon-coated ferroferric oxide magnetic microspheres (FC3) prepared in the example 1 of the invention and the yeast carbon-coated ferroferric oxide magnetic microspheres modified bismuth oxyiodide composite photocatalytic material (BF2C3), the pure bismuth oxyiodide (BiOI) material prepared in the comparative example 1 and the pure ferroferric oxide nano-microspheres (Fe) prepared in the comparative example 23O4) X-ray diffraction characterization analysis was performed, and the results are shown in FIG. 1. As can be seen from FIG. 1, Fe3O4The diffraction peaks of the crystalline phase (2 theta) appear at positions of 30.24 degrees, 35.59 degrees, 43.19 degrees, 57.32 degrees and 62.60 degrees, and the diffraction peaks accord with the classical diffraction peaks of the traditional magnetite (JCPDS card No.19-629), while the addition of yeast carbon to Fe in FC33O4Has no influence on the formation of (2), and the yeast carbon does not form a specific diffraction peak.Pure bismuth oxyiodide material (BiOI) shows peaks at diffraction angles of 29.74 °,31.71 °,37.2 °,39.5 °,45.8 °,51.5 °,55.3 °, and corresponds to (012), (110), (013), (004), (020), (014), (122) planes (JCPDS No.10-0445) in the bismuth oxyiodide crystal form, respectively. In an X-ray diffraction pattern of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3), Fe is contained3O4And diffraction peaks of BiOI, indicating Fe3O4And BF2C3 are tightly combined in the synthesis process, so that BiOI @ Fe is successfully prepared3O4@ C composite photocatalytic material.
Scanning electron microscope and transmission electron microscope analysis were performed on the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, and the results are shown in fig. 2 and fig. 3. Fig. 2 is a scanning electron microscope image of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention. Fig. 3 is a transmission electron microscope image of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention. As can be seen from FIGS. 2 and 3, in the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material prepared by the method, Fe is contained3O4Is in the form of microspheres with a diameter of about 200nm, surrounded by a thin, light-colored yeast carbon layer, and Fe3O4The @ C microspheres are uniformly dispersed around the bismuth oxyiodide microspheres, and the bismuth oxyiodide is flocculent pompon with the diameter close to 2 mu m.
Ultraviolet-visible light diffuse reflection absorption spectrum analysis was performed on the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, the pure bismuth oxyiodide (bio) material prepared in comparative example 1, and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2, and the results are shown in fig. 4. As can be seen from fig. 4, pure bio i only generates light absorption in the visible and infrared wavelength ranges, whereas BF2 has a slightly lower light absorption intensity in the light wavelength range but a wider light absorption region than pure bio i, and still generates light absorption in the near infrared wavelength range. And the optical spectrogram shown by the BF2C3 composite photocatalytic material is red-shifted relative to pure BiOI and BF2, so that the optical absorption intensity is higher, the optical absorption wavelength is wider, and the separation and the generation of photon-generated carriers are more facilitated. After the yeast carbon-coated ferroferric oxide magnetic microspheres are loaded on bismuth oxyiodide, the forbidden band width of the yeast carbon-coated ferroferric oxide magnetic microspheres is reduced from the original 1.78eV (BiOI) to 1.47eV (BF2C3), so that the response degree of the material to visible light is promoted.
The yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in the embodiment 1 of the invention, the pure bismuth oxyiodide (BiOI) material prepared in the comparative example 1 and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in the comparative example 2 are subjected to surface-induced current analysis of a semiconductor, and the result is shown in FIG. 5. As can be seen from fig. 5, the photocurrent intensity generated by the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material under the irradiation of the same visible light condition is obviously higher than that of the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material prepared in the comparative example 2, and both the photocurrent intensity and the photocurrent intensity are higher than that of the pure bismuth oxyiodide composite material prepared in the comparative example 1, which fully indicates that the existence of the ferroferric oxide nano-microspheres and the yeast carbon can effectively enhance the transfer and separation of carriers generated by the BiOI under the irradiation condition, thereby improving the photocatalytic performance in the whole system.
Impedance analysis of a semiconductor was performed on the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in example 1 of the present invention, the pure bismuth oxyiodide (bio) material prepared in comparative example 1, and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in comparative example 2, and the results are shown in fig. 6. As shown in FIG. 6, the radii of the impedance curves generated in the three materials are BiOI > BF2> BF2C3 in sequence, which shows that compared with a pure bismuth oxyiodide material and a pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material, the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) has the highest separation efficiency of photohole electron pairs and the fastest charge transfer speed.
Comparative example 3
The photocatalytic degradation effect of the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material on the antibiotic tetracycline wastewater is investigated.
The pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF1, BF2, BF4 and BF8) prepared in the comparative example 2 and the pure BiOI prepared in the comparative example 1 are applied to tetracycline wastewater photocatalytic degradation treatment, and the steps are as follows: respectively weighing 50mg of BF1, BF2, BF4 and BF8 composite photocatalytic materials prepared in the comparative example 2 and pure BiOI prepared in the comparative example 1 in a tetracycline simulation waste water solution with the volume of 50mL and the concentration of 30mg/L, oscillating for 1h under the condition of keeping out of the sun to enable the materials to reach adsorption balance, then carrying out photocatalytic degradation reaction under the irradiation conditions of visible light LEDs and the like (lambda is greater than 420nm), wherein the reaction time is 90min, sampling and carrying out solid-liquid separation on a polyether sulfone filter membrane at 10min, 20min, 40min, 60min and 90min respectively in the reaction process, measuring the concentration of the residual antibiotic tetracycline in the filtrate at 357nm by using an ultraviolet spectrophotometer, and calculating the residual rate of the tetracycline. In this example, 1 tetracycline solution without any catalytic material, with a volume of 50mL and a concentration of 30mg/L was set as a control for blank comparison. The degradation effect of different pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic materials on tetracycline under visible light conditions is shown in figure 7. As can be seen from FIG. 7, tetracycline remains stable under only visible light conditions and does not undergo degradation reactions. 57.32 percent of pure BiOI remains in the system after 90min of tetracycline degradation, and the degradation efficiency is only 42.68 percent. After the tetracycline is degraded for 90min under visible light by adopting BF1, BF2, BF4 and BF8 synthetic materials, the residual rates of the tetracycline in the system are respectively 20.21%, 16.37%, 29.36% and 37.28%. The corresponding tetracycline degradation rates were 79.79%, 83.63%, 70.64% and 62.72%, respectively. The doping of the ferroferric oxide nano-microspheres can effectively promote the photocatalytic response of the bismuth oxyiodide material and the degradation of the bismuth oxyiodide material to the antibiotic pollution.
Example 2
The photocatalytic degradation effect of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material on the antibiotic tetracycline wastewater is examined.
The yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C2, BF2C3, BF2C4 and BF2C5) prepared in the example 1 is applied to tetracycline wastewater photocatalytic degradation treatment, and the implementation steps are the same as those in the example 2: respectively weighing 50mg of the BF2C2, BF2C3, BF2C4 and BF2C5 composite photocatalytic materials prepared in example 1 in 50mL of tetracycline simulation waste water solution with the concentration of 30mg/L, oscillating for 1h under the condition of keeping out of the sun to enable the materials to reach adsorption balance, then carrying out photocatalytic degradation reaction under the irradiation conditions of visible light LEDs and the like (lambda is greater than 420nm), wherein the reaction time is 90min, sampling and carrying out solid-liquid separation on a polyether sulfone filter membrane at 10min, 20min, 40min, 60min and 90min respectively in the reaction process, measuring the concentration of the residual antibiotic tetracycline in the filtrate at 357nm by using an ultraviolet spectrophotometer, and calculating the residual rate of the tetracycline. In this example, four different yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic materials are compared with the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) having the best tetracycline catalytic degradation effect in example 2. The degradation effect of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material for tetracycline under visible light conditions is shown in fig. 8. As can be seen from FIG. 8, under the condition of the same molar ratio of iron to bismuth, different amounts of carbon in yeast can lead to different catalytic degradation effects of the finally obtained composite photocatalytic material. When the adding amount of yeast in the carbon-coated ferroferric oxide magnetic microsphere precursor is 0.2-0.3 g, the photocatalytic degradation rate of the finally synthesized composite photocatalytic material to tetracycline is increased along with the increase of the adding amount of the yeast; however, when the adding amount of the yeast is more than 0.3g, the photocatalytic degradation rate of the finally synthesized composite photocatalytic material to tetracycline is reduced along with the further increase of the adding amount of the yeast. And the photocatalytic degradation rate of BF2C2, BF2C3 and BF2C4 to tetracycline is better than BF2, but the degradation rate of BF2C5 to tetracycline is lower than BF 2. After the 4 composite photocatalytic materials BF2C2, BF2C3, BF2C4 and BF2C5 are irradiated for 90min by visible light, the residual rates of tetracycline in the solution are 14.91%, 9.4%, 12.81% and 21.39%, and the corresponding degradation rates are 85.09%, 90.6%, 87.19% and 79.61% respectively. The doping of the yeast carbon can effectively promote the degradation of the final synthetic material to the antibiotics, but the adding amount of the yeast carbon in the precursor needs to be controlled.
Example 3
The photocatalytic degradation effect of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material on ciprofloxacin wastewater is examined.
The yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in the embodiment 1 of the invention, the pure bismuth oxyiodide (BiOI) prepared in the comparative example 1 and the pure ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2) prepared in the comparative example 2 are applied to ciprofloxacin wastewater photocatalytic degradation treatment, and the implementation steps are similar to those in the embodiment 2: respectively weighing 50mg of BF2C3, BiOI and BF2 photocatalytic materials prepared in example 1, comparative example 1 and comparative example 2 in ciprofloxacin simulated wastewater solution with the volume of 50mL and the concentration of 10mg/L, oscillating for 1h under the condition of keeping out of the sun to achieve adsorption balance, then carrying out photocatalytic degradation reaction under the irradiation conditions (lambda is more than 420nm) of a visible light LED and the like for 120min, sampling and carrying out solid-liquid separation on a polyether sulfone filter membrane at 10min, 20min, 40min, 60min, 90min and 120min in the reaction process, measuring the concentration of the residual antibiotic ciprofloxacin in the filtrate at 276nm by using an ultraviolet spectrophotometer, and calculating the residual rate of the ciprofloxacin. In the implementation, 1 ciprofloxacin solution which is not added with any catalytic material, has the volume of 50mL and the concentration of 10mg/L is set as a control group for blank comparison. The degradation effect of different composite photocatalytic materials on ciprofloxacin under the condition of visible light is shown in figure 9. As can be seen from fig. 9, only visible light irradiation conditions had negligible effect on degradation of ciprofloxacin. And the residue rates of ciprofloxacin in a system after the BiOI, BF2 and BF2C3 three synthetic materials degrade ciprofloxacin for 2h under the same condition are respectively 67%, 38.43% and 28.88%, which respectively correspond to the degradation rates of 33%, 61.57% and 71.12%. The modification of the bismuth oxyiodide microspheres by the yeast carbon and the ferroferric oxide nano microspheres is beneficial to the degradation of the composite photocatalytic material responding to visible light to the antibiotic ciprofloxacin, and the promotion effect is benefited by the synergistic effect between the yeast carbon and the ferroferric oxide. With reference to example 3, it is fully demonstrated that the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material synthesized by the method can effectively utilize a visible light source to degrade different types of antibiotics.
Example 4
The catalytic stability of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) is examined.
(1) Weighing 50mg of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared in the example 1, adding the weighed material into 50mL of tetracycline waste liquid with the concentration of 30mg/L, oscillating and adsorbing for 1h under the condition of keeping out of the sun to achieve adsorption balance, and then carrying out catalytic degradation reaction under the irradiation of a pure visible light LED lamp for 90 min. After the reaction is finished, centrifugally collecting the BF2C3 composite photocatalytic material, cleaning the composite photocatalytic material for 3 times by using ultrapure water, and then drying and regenerating the composite photocatalytic material in vacuum at the temperature of 60 ℃. The completely dried BF2C3 was taken out, the tetracycline degradation reaction was repeated under the same catalytic conditions as described above and BF2C3 was regenerated in the same manner after completion of the reaction, and this operation was repeated four times.
And centrifuging and collecting the residual tetracycline solution after each cyclic utilization and degradation, detecting the residual concentration of the tetracycline solution at 357nm by using an ultraviolet spectrophotometer, and calculating the residual rate of the BF2C3 composite photocatalytic material for catalyzing and degrading the tetracycline in each cycle, wherein the result is shown in FIG. 10. As can be seen from FIG. 10, the catalytic degradation efficiency of the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material (BF2C3) prepared by the method can still reach 78.1% under the condition of visible light after 4 times of complete cyclic utilization, so that the yeast carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material synthesized by the method has stable catalytic degradation performance, is not easy to corrode in the application process, and can be repeatedly applied.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material is characterized by comprising the following steps of:
(1) adding yeast into the ferroferric oxide precursor solution, uniformly mixing, and then performing hydrothermal carbonization for 12-14 h at 180-200 ℃ to obtain carbon-coated ferroferric oxide magnetic microspheres;
(2) mixing carbon-coated ferroferric oxide magnetic microspheres and bismuth nitrate pentahydrate according to the molar ratio of iron to bismuth of 1: (1-8) adding the mixture into an alcohol solvent, uniformly mixing, adding potassium iodide, heating for reaction, naturally cooling, continuing to react, washing and drying to obtain BiOI @ Fe3O4@ C composite photocatalytic material;
adding the yeast into the ferroferric oxide precursor solution in the form of yeast freeze-dried powder, wherein the mass ratio of the yeast freeze-dried powder to the ferroferric oxide precursor in the ferroferric oxide precursor solution is (0.2-0.5): 2.5, wherein the ferroferric oxide precursor is FeCl3·6H2O；
The ferroferric oxide precursor solution in the step (1) is FeCl3·6H2O, anhydrous sodium acetate and sodium acrylate according to a mass ratio of 2.5: 3.4: 3.4 mixing the resulting mixed solution.
2. The preparation method of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material as claimed in claim 1, wherein the molar ratio of bismuth nitrate pentahydrate to potassium iodide in the step (2) is 1: 1; the heating reaction temperature is 80 ℃, and the time is 3 h.
3. The preparation method of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material as claimed in claim 2, wherein the preparation method is characterized in thatIn that FeCl is present in the mixed solution3·6H2The concentration of O is 55.5-62.5 g/L;
the concentration of the bismuth nitrate pentahydrate in the alcohol solvent in the step (2) is 25-48.5 g/L; the potassium iodide is added in the form of a potassium iodide aqueous solution, and the concentration of the potassium iodide is 33-49.5 g/L.
4. The preparation method of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material as claimed in claim 1, wherein the yeast in the step (1) is pichia pastoris; the mixing is ultrasonic mixing, and the ultrasonic mixing time is 60-90 min;
the mixing condition in the step (2) is that oscillation reaction is carried out for 30-60 min at the temperature of 25-35 ℃ and the rpm of 150-180;
and the time for naturally cooling and continuously reacting is 5-8 h, and the reaction is carried out under the oscillation condition.
5. The preparation method of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material as claimed in claim 1, wherein the carbon-coated ferroferric oxide magnetic microsphere is obtained by performing hydrothermal carbonization, washing with water, and drying at 60 ℃ for 12h in the step (1); the solvent of the ferroferric oxide precursor solution is a mixed solvent of ethylene glycol and diethylene glycol with the volume ratio of 1: 1;
the alcohol solvent in the step (2) is ethylene glycol; the heating reaction is carried out under the oscillation condition; the washing is respectively carried out by using ethanol and water, the drying temperature is 60-80 ℃, and the drying time is 12-14 h.
6. The carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material prepared by the method of any one of claims 1 to 5.
7. The application of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material in the field of photocatalytic degradation.
8. According to the rightThe application of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material in the field of photocatalytic degradation is claimed in claim 7, and the application is the application in treatment of antibiotic wastewater, and the method comprises the following steps: adding BiOI @ Fe3O4The @ C composite material is mixed with the antibiotic wastewater, the mixture is oscillated for a certain time under the condition of keeping out of the sun to achieve adsorption balance, and then photocatalytic degradation is carried out under the condition of visible light to complete the degradation treatment of the antibiotic wastewater.
9. The application of the carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material in the field of photocatalytic degradation is characterized in that the BiOI @ Fe3O4The dosage of the @ C composite material in the antibiotic wastewater is 0.6-1 g/L; the antibiotics in the antibiotic wastewater are at least one of tetracycline, ciprofloxacin and amoxicillin; the concentration of the antibiotic wastewater is 10-30 mg/L; the oscillation time is 0-60 min;
the photocatalytic degradation is carried out under the conditions of low-energy-consumption LED lamp illumination with the power of 5W and the pH of the antibiotic wastewater; the time of the photocatalytic degradation is 10-120 min.
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| CN106563431A (en) * | 2016-11-07 | 2017-04-19 | 杭州同净环境科技有限公司 | Composite photocatalyst, preparation method and application thereof |
| CN108654650A (en) * | 2018-03-19 | 2018-10-16 | 启东创绿绿化工程有限公司 | It is a kind of to prepare BiOI/Fe3O4The method of catalysis material |
| CN109718812A (en) * | 2017-10-31 | 2019-05-07 | 香港科技大学 | A kind of visible optical driving type photocatalyst composite particle of magnetism and its preparation and application |
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| CN106563431A (en) * | 2016-11-07 | 2017-04-19 | 杭州同净环境科技有限公司 | Composite photocatalyst, preparation method and application thereof |
| CN109718812A (en) * | 2017-10-31 | 2019-05-07 | 香港科技大学 | A kind of visible optical driving type photocatalyst composite particle of magnetism and its preparation and application |
| CN108654650A (en) * | 2018-03-19 | 2018-10-16 | 启东创绿绿化工程有限公司 | It is a kind of to prepare BiOI/Fe3O4The method of catalysis material |
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