CN111760569A - Composite photo-Fenton catalyst, preparation method and application - Google Patents
Composite photo-Fenton catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004098 Tetracycline Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229960002180 tetracycline Drugs 0.000 claims description 6
- 229930101283 tetracycline Natural products 0.000 claims description 6
- 235000019364 tetracycline Nutrition 0.000 claims description 6
- 150000003522 tetracyclines Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052603 melanterite Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 230000033558 biomineral tissue development Effects 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 27
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- UFXGQUPBYNXNEW-UHFFFAOYSA-N photo-fenton reagent Chemical compound C1=CC(C(N(CC(OC)OO)C2=O)=O)=C3C2=CC=C2C(=O)N(CC(OC)OO)C(=O)C1=C32 UFXGQUPBYNXNEW-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/34—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
- C02F2101/38—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
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Abstract
The invention discloses a composite photo-Fenton catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing Fe3O4(ii) a Is prepared into g-C3N4(ii) a G to C3N4Dissolving in deionized water, and ultrasonic treating to obtain g-C3N4A suspension; mixing Fe3O4Dissolved in the solvent to removeIn the sub-water, the Fe is obtained by ultrasonic treatment3O4Suspending the solution, then adding Fe3O4The suspension is added dropwise to g-C3N4The suspension is hermetically stirred for 24 hours to obtain an initial solution, the initial solution is centrifuged and washed, and the initial solution is dried in vacuum at 60 ℃ for 24 hours to obtain the composite photo-Fenton catalyst; the composite Fenton photocatalyst synthesized by the method has the characteristics of magnetism, easiness in separation and recovery, high stability, strong reusability and strong mineralization capability, and the Fe synthesized by the method3O4The nano-particles expose more {110} crystal faces, so that the photocatalytic performance of the nano-particles is better.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite photo-Fenton catalyst, a preparation method and application thereof.
Background
The ubiquitous of antibiotics in water environment poses potential threats to human health and ecological environment, so that the removal of trace antibiotics in water becomes an urgent problem to be solved. In the actual process of processing the tetracycline, due to the complexity of post-processing and the antibacterial property of the tetracycline, the traditional technologies such as physical adsorption and biodegradation are difficult to completely remove.
Advanced Oxidation (AOPS) technology is taken as a type of rich-form, high-speed and high-efficiency treatment technology for removing tetracycline in water body, including UV/H2O2、H2O2/Fe2+, and UV/g-C3N4And the like. Among them, the hydroxyl radical generated by the conventional fenton reaction can effectively remove tetracycline, but has some fatal disadvantages such as: iron mud, high iron consumption, low pH, etc.; g-C3N4The photocatalyst has a narrow forbidden band of 2.7eV, can be used as a visible light photocatalyst, but the photocatalytic performance of the photocatalyst is influenced due to the high photo-generated electron-hole recombination rate.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of the composite photo-Fenton catalyst, which comprises the following steps:
s1, FeSO4·7H2O and Na2S2O3·5H2Dissolving O in deionized water to obtain a first aqueous solution, dissolving NaOH in deionized water to obtain a second aqueous solution, mixing and stirring the first aqueous solution and the second aqueous solution to obtain a reaction solution, transferring the reaction solution into a high-pressure kettle, sealing and keeping at 140 ℃ for 12 hours, cooling to room temperature, washing with deionized water for 3-4 times, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain Fe3O4；
S2, placing urea in a crucible, heating to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling to room temperature, and grinding to obtain g-C3N4；
S3, mixing g-C3N4Dissolving in deionized water, and ultrasonic treating to obtain g-C3N4A suspension; mixing Fe3O4Dissolving in deionized water, and performing ultrasonic treatment to obtain Fe3O4Suspending the solution, then adding said Fe3O4Adding the suspension dropwise to the g-C3N4And (3) sealing and stirring the suspension for 24h to obtain an initial solution, centrifuging and washing the initial solution, and drying the initial solution at 60 ℃ in vacuum for 24h to obtain the composite photo-Fenton catalyst.
Preferably, during the preparation of the first aqueous solution, FeSO4·7H21.20 to 3.50g of O and Na2S2O3·5H21.10-2.50 g of O and 15-30 mL of deionized water.
Preferably, in the preparation process of the second aqueous solution, 0.2g to 0.4g of NaOH and 10mL to 30mL of deionized water are used.
Preferably, in step S1, the mixing and stirring time of the first aqueous solution and the second aqueous solution is 3 to 7 min.
Preferably, in the step S3, 90 to 99mg of g-C is added3N4Dissolving in 50mL deionized water, and adding 1 mg-10 mg Fe3O4Dissolved in 10mL of deionized water.
Preferably, the composite photo-Fenton catalyst and the preparation method thereofPreparing, the compound photo-Fenton catalyst is Fe3O4/g-C3N4。
Preferably, the application of the composite photo-Fenton catalyst is used for removing tetracycline in a water body.
Compared with the prior art, the invention has the beneficial effects that: the invention is under visible light condition, Fe3O4/g-C3N4Catalyzing hydrogen peroxide to generate hydroxyl free radicals and superoxide free radicals to degrade tetracycline hydrochloride. The composite Fenton photocatalyst synthesized by the method has the characteristics of magnetism, easiness in separation and recovery, high stability, strong reusability and strong mineralization capability, and the Fe synthesized by the method3O4The nano-particles expose more {110} crystal faces, so that the photocatalytic performance of the nano-particles is better. Within 100min, Fe3O4/g-C3N4Can degrade the total organic carbon of the tetracycline hydrochloride by 67.1 percent, so that the tetracycline hydrochloride is converted into harmless micromolecular substances. In addition, five times of repeated experiments show that the removal rate can reach 87.9 percent, which indicates that Fe3O4/g-C3N4Has excellent activity, low leaching rate of iron and good stability. In the invention, Fe3O4/g-C3N4The product has good application prospect when used as a photo-Fenton reagent for treating tetracycline antibiotics in water.
Drawings
FIG. 1 is Fe3O4/g-C3N4Scanning electron microscope images of;
FIG. 2 shows Fe generated in step S13O4Scanning an electron microscope;
FIG. 3 shows Fe produced by the present invention3O4/g-C3N4And ordinary Fe3O4/g-C3N4A degradation rate comparison graph of tetracycline hydrochloride under visible light;
FIG. 4 shows Fe produced by the present invention3O4/g-C3N4A comparison graph of the influence of the photo-Fenton material on the degradation of tetracycline hydrochloride under different pH states;
FIG. 5 shows Fe produced by the present invention3O4/g-C3N4photo-Fenton materials in different H2O2A comparison graph of the influence of the dosage on the degradation of tetracycline hydrochloride;
FIG. 6 shows Fe produced by the present invention3O4/g-C3N4A comparison graph of the removal rates of tetracycline hydrochloride and total organic carbon after five recycles;
FIG. 7 shows Fe produced by the present invention3O4/g-C3N4And (3) a comparative graph of reaction degradation under solar illumination and visible light illumination.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example one
The composite photo-Fenton catalyst is Fe3O4/g-C3N4photo-Fenton material, said Fe3O4/g-C3N4The preparation method of the photo-Fenton material specifically comprises the following steps:
s1, mixing 1.39g of FeSO4·7H2O and 1.24gNa2S2O3·5H2O was dissolved in 15mL of deionized water, 0.4g of naoh was dissolved in 10mL of deionized water, and after mixing and stirring the two for about 5min, the reacted solution was transferred to a 50mL autoclave, sealed and maintained at 140 ℃ for 12 hours, and then cooled to room temperature. Finally, washing the mixture for 3-4 times by using deionized water, and drying the mixture for 4 hours in a vacuum oven at the temperature of 60 ℃ to prepare Fe3O4。
S2, placing 15g of urea in a crucible, heating the urea in a muffle furnace at a heating rate of 5 ℃/min to 550 ℃, keeping the temperature for 2 hours, cooling to room temperature, and grinding to obtain g-C3N4。
S3, mixing 93mg of g-C3N4Dissolving in 50mL deionized water, and performing ultrasonic treatment for 30 min; mixing 7mgFe3O4Dissolved in 10mL deionized water and sonicated for 15 min. Then Fe3O4The suspension is added dropwise to g-C3N4Suspending liquid, sealing and stirring for 24h, centrifuging and washing the obtained product, and drying the product in vacuum at 60 ℃ for 24h to obtain Fe3O4/g-C3N4。
As shown in FIG. 1, FIG. 1 shows Fe3O4/g-C3N4Scanning electron micrograph of (A), Fe prepared by the present invention3O4/g-C3N4Is powdery, has larger specific surface area and more active sites.
As shown in FIG. 2, FIG. 2 shows Fe generated in step S13O4Scanning electron microscope. It can be seen that Fe produced by the present invention3O4It is polyhedral and has 11 {110} crystal planes, 8 {111} crystal planes and 6 {100} crystal planes. In general, the final size and shape of the micro-nanocrystals are the result of competition between nucleation and growth during the crystal growth phase, both of which are determined by the intrinsic crystal structure of the product and the chemical potential of the reaction process. The key factor for regulating and controlling the morphology of the nano-particles is controlling the growth direction of a crystal face, Fe3O4 belongs to a face-centered cubic structure from the crystallographic point of view, and the method obeys the following crystal face energy rule: γ {111} < γ {100} < γ {110 }. This also indicates that the 111 crystal plane is in the lowest energy state, the 110 crystal plane is in the highest energy state, and the 100 crystal plane is in between. Therefore, Fe produced by the present invention3O4Compared with the common spherical Fe3O4The particles expose more high-energy 110 crystal faces, and the photocatalysis performance is better.
FIG. 3 shows Fe produced by the present invention3O4/g-C3N4And ordinary Fe3O4/g-C3N4A graph comparing the degradation rate of tetracycline hydrochloride under visible light. As shown in the figure, the {110} -Fe generated by the invention3O4/g-C3N4Middle Fe3O4The {110} crystal face with high energy is exposed, the photocatalysis performance is better than that of the common Fe3O4Synthetic Fe3O4/g-C3N4The degradation rate of the tetracycline hydrochloride is improved by 40.2 percent within 100 minutes.
Example two
Fe3O4/g-C3N4The specific test process of degrading tetracycline hydrochloride in water by using the photo-Fenton material comprises the following steps:
a1, adjusting the pH of tetracycline hydrochloride solution, and adding a certain amount of Fe3O4/g-C3N4Add 50mL tetracycline hydrochloride solution and stir in the dark for 30 min.
A2, adding a certain amount of H2O2The reaction was started for 100min and 1mL of the reaction suspension was sampled every 20 min. The obtained sample was filtered, and the tetracycline hydrochloride concentration was measured.
In the removal of tetracycline hydrochloride, Fe3O4/g-C3N4The addition amount of (B) is 0.5 g/L-2.0 g/L.
When the tetracycline hydrochloride is removed, the initial concentration of the tetracycline hydrochloride in the system is 25 mg/L-85 mg/L.
FIG. 4 is a graph showing Fe produced by the present invention, as shown in FIG. 43O4/g-C3N4A comparison graph of the influence of the photo-Fenton material on the degradation of tetracycline hydrochloride under different pH states; the composite photo-Fenton catalyst has a tetracycline hydrochloride removal rate of over 90% under the condition that the pH value is 2-5. Even under the condition that the pH value is close to neutrality, the removal rate can reach 70-80%. As can be seen from fig. 4, the composite photo-fenton catalyst of the present invention has a low pH, which increases the application range of the photo-fenton catalyst, realizes the reaction without adjusting the pH, and reduces the operation cost.
FIG. 5 shows Fe produced by the present invention3O4/g-C3N4photo-Fenton materials in different H2O2A comparison graph of the influence of the dosage on the degradation of tetracycline hydrochloride; as shown in the figure, the composite photo-Fenton catalyst of the invention is in H2O2Under the condition of 5mmol/L, the removal rate of tetracycline hydrochloride reaches 98 percent. And at H2O2Under the condition of 3mmol/L, the removal rate can reach 95 percent. While the conventional homogeneous Fenton reaction generally requires H2O2The concentration is 10 mmol/L-20 mmol/L, the catalyst H is used2O2The concentration only needs 3 mmol/L-5 mmol/L, which reduces the operation cost.
FIG. 6 shows Fe produced by the present invention3O4/g-C3N4A comparison graph of the removal rates of tetracycline hydrochloride and total organic carbon after five recycles; after five recycles, Fe3O4/g-C3N4Still has strong activity to the degradation and mineralization of tetracycline hydrochloride. After six uses, the degradation efficiency of the tetracycline hydrochloride is from 98.8% to 87.9%, and the mineralization degree of the tetracycline hydrochloride is from 67.1% to 57.1%. This indicates that Fe3O4/g-C3N4The compound has good stability and reusability when being used as a photo-Fenton reagent to degrade tetracycline hydrochloride.
FIG. 7 shows Fe produced by the present invention3O4/g-C3N4And (3) a comparative graph of reaction degradation under solar illumination and visible light illumination. The reaction is carried out for 60min under the sun illumination, the degradation efficiency of the tetracycline hydrochloride is 99.7 percent, and the reaction is quicker than that under the visible light illumination, which shows that Fe3O4/g-C3N4The method has better practical application prospect when being used as a photo-Fenton reagent to degrade tetracycline hydrochloride.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of the composite photo-Fenton catalyst is characterized by comprising the following steps:
s1, FeSO4·7H2O and Na2S2O3·5H2Dissolving O in deionized water to obtain a first aqueous solution, dissolving NaOH in deionized water to obtain a second aqueous solution, mixing and stirring the first aqueous solution and the second aqueous solutionObtaining a reaction solution, transferring the reaction solution into an autoclave, sealing and keeping the autoclave at 140 ℃ for 12 hours, then cooling to room temperature, finally washing with deionized water, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain Fe3O4；
S2, placing urea in a crucible, heating to 550 ℃ in a muffle furnace at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling to room temperature, and grinding to obtain g-C3N4；
S3, mixing g-C3N4Dissolving in deionized water, and ultrasonic treating to obtain g-C3N4A suspension; mixing Fe3O4Dissolving in deionized water, and performing ultrasonic treatment to obtain Fe3O4Suspending the solution, then adding said Fe3O4Adding the suspension dropwise to the g-C3N4And (3) sealing and stirring the suspension for 24h to obtain an initial solution, centrifuging and washing the initial solution, and drying the initial solution at 60 ℃ in vacuum for 24h to obtain the composite photo-Fenton catalyst.
2. The method of preparing a composite photo-Fenton catalyst according to claim 1, wherein in the preparation of the first aqueous solution, FeSO is added4·7H21.20 to 3.50g of O and Na2S2O3·5H21.10-2.50 g of O and 15-30 mL of deionized water.
3. The method for preparing the composite photo-Fenton catalyst according to claim 1, wherein in the preparation process of the second aqueous solution, NaOH is 0.2g to 0.4g, and deionized water is 10mL to 30 mL.
4. The method for preparing a composite photo-Fenton catalyst according to claim 1, wherein in the step S1, the mixing and stirring time of the first aqueous solution and the second aqueous solution is 3min to 7 min.
5. The method of preparing a composite photo-Fenton catalyst according to claim 1, wherein said method comprises the steps ofIn the step S3, 90 to 99mg of g-C3N4Dissolving in 50mL deionized water, and adding 1 mg-10 mg Fe3O4Dissolved in 10mL of deionized water.
6. A composite photo-Fenton catalyst prepared by the method of any one of claims 1 to 5, wherein the composite photo-Fenton catalyst is Fe3O4/g-C3N4。
7. Use of the composite photo-Fenton catalyst according to claim 6, for the removal of tetracycline from an aqueous body.
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| CN202010659585.3A CN111760569A (en) | 2020-07-08 | 2020-07-08 | Composite photo-Fenton catalyst, preparation method and application |
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