CN115121249A - Preparation method and application of magnetic sodium iron silicate/hematite composite photocatalyst - Google Patents
Preparation method and application of magnetic sodium iron silicate/hematite composite photocatalyst Download PDFInfo
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- CN115121249A CN115121249A CN202210604019.1A CN202210604019A CN115121249A CN 115121249 A CN115121249 A CN 115121249A CN 202210604019 A CN202210604019 A CN 202210604019A CN 115121249 A CN115121249 A CN 115121249A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052595 hematite Inorganic materials 0.000 title claims abstract description 16
- 239000011019 hematite Substances 0.000 title claims abstract description 16
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 229910000859 α-Fe Inorganic materials 0.000 claims description 32
- 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 claims description 12
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 229920005630 polypropylene random copolymer Polymers 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000004098 Tetracycline Substances 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 229960002180 tetracycline Drugs 0.000 abstract 1
- 229930101283 tetracycline Natural products 0.000 abstract 1
- 235000019364 tetracycline Nutrition 0.000 abstract 1
- 150000003522 tetracyclines Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
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- 239000012190 activator Substances 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
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- 230000007281 self degradation Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- B01J35/33—
-
- B01J35/39—
-
- 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
- C02F2101/38—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
A preparation method and application of a magnetic sodium iron silicate/hematite composite photocatalyst relate to the field of photocatalytic sewage treatment. The formula raw materials used in the invention are as follows: diatomite, ferric nitrate nonahydrate, glycol and sodium hydroxide. The method comprises the following steps: adding NaOH into a mixed solution of ethylene glycol and water, stirring to dissolve, then respectively adding diatomite and ferric nitrate nonahydrate into the solution, stirring for a certain time, transferring the mixed solution raw material into a PPL lining in a high-pressure reaction kettle, then placing the PPL lining in a drying oven, and keeping the PPL lining at 200 ℃ for 12 hours. To be cooledAfter cooling to room temperature, the mixture was washed several times with deionized water and ethanol. The magnetic sodium iron silicate/hematite composite photocatalyst is applied to visible light and H 2 O 2 Under the combined action, performing photo-Fenton degradation on the tetracycline solution; has good development prospect and industrial application potential.
Description
Technical Field
The invention relates to the field of photocatalytic sewage treatment. In particular to a preparation method and application of a magnetic sodium iron silicate/hematite composite photocatalyst.
Background
With the rapid development of the pharmaceutical industry, the excessive discharge of antibiotic wastewater from pharmaceutical factories seriously threatens the ecological balance and human health, and is considered as a new generation of organic pollutants in water. The Fenton (Fenton) technology is an environment-friendly and efficient Advanced Oxidation Process (AOPs), and has a wide application prospect in removing water pollutants, especially antibiotics. However, the traditional homogeneous Fenton technology has serious defects which are mainly represented by continuous supply of a reducing agent Fe (II), non-recyclable iron ions, narrow pH range (about 4), secondary pollution of iron mud and the like. To address this challenge, a photo-Fenton-like technique, which is an effective combination of Fenton technology and semiconductor photocatalysts, can improve catalytic efficiency and reduce costs. The photo-Fenton catalysts used so far mainly comprise iron-based and copper-based semiconductors. The photo-Fenton advantage of the Fe-based semiconductor system is that the conversion of Fe (III) to Fe (II) is achieved by photoinduced electrons, while H 2 O 2 Reduced by Fe (II) to form high oxidation potential OH radicals (E) 0 2.80 eV/SHE). In addition, the heterogeneous photo-Fenton system has the advantages of good reutilization, high catalytic efficiency, wide application range and no secondary pollution. The photo-assisted Fenton catalytic technology has become a wide and promising research hotspot as another extension of the photocatalytic technology.
The development of a novel photocatalyst is the core and essence of a photo-Fenton catalytic technology. Most of the existing photocatalysts have the defects of low photocatalytic activity under visible light, unreusable property, difficulty in separation from a solution, high cost, high toxicity and the like, so that the practical application of the photocatalysts is seriously hindered. Therefore, the novel visible light drive photocatalyst which has high synthesis activity, good stability, easy recovery, low cost and no toxicity has very important significance.
Of the numerous semiconductor photocatalysts, hematite (α -Fe) 2 O 3 ) The catalyst has narrow band gap (2.0 eV), low cost, large photoresponse range and excellent catalytic performance, and thus is widely applied to the field of photo-Fenton catalysis. However, the pure phase catalyst has high recombination efficiency of photo-generated carriers, and therefore further modification treatment is required. Wherein the construction of the heterojunction compound to enhance the separation efficiency of the photogenerated carriers is a simple and effective way. The key point in constructing a heterojunction is that the energy band positions are matched, so that the band-to-band transfer of carriers can be realized. Silicate semiconductor materials are novel photocatalysts with great application potential due to the advantages of various components, low price, environmental friendliness and the like, wherein iron-based photocatalysts, namely Sodium iron silicate (SFS), can be applied to fenton-like systems to pay attention. But pure phase of alpha-Fe 2 O 3 The photocatalyst has low performance due to the defects of serious carrier recombination with sodium ferric silicate, small light absorption range and the like, and therefore modification treatment is needed.
The heterogeneous photo-Fenton catalyst which has high cost performance, environmental friendliness, high catalytic efficiency, good durability and good stability and is convenient to recover is developed, and has important significance and necessity for treating antibiotic wastewater. Therefore, further conversion of alpha-Fe is required 2 O 3 And SFS composite modification to improve the photocatalytic performance of the material. At the same time, magnetic material Fe is introduced into the compound 3 O 4 Preparation of magnetic sodium iron silicate/hematite (M-SFS/alpha-Fe) 2 O 3 ) The compound makes the catalyst more convenient to recycle.
Disclosure of Invention
The invention aims to provide a magnetic M-SFS/alpha-Fe 2 O 3 The preparation method and the application of the photocatalyst have the characteristics of easily obtained raw materials, simple and convenient steps, high performance, easy recycling and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
firstly, adding NaOH into a mixed solution of ethylene glycol and water, sequentially adding diatomite and ferric nitrate nonahydrate, stirring uniformly, transferring into a PPL (polypropylene random copolymer) lined high-pressure reaction kettle, and preparing a magnetic M-SFS/alpha-Fe 2O3 photocatalyst by hydrothermal method; then washed and dried.
The mass ratio of the diatomite to the ferric nitrate nonahydrate is 1: 50-200. The concentration of sodium hydroxide in the mixed solution is 5-50 g/L; the volume ratio of ethylene glycol to water was 3: (1-3); the hydrothermal condition is 180 ℃ and 200 ℃ for 10-20 h. The specific conditions for drying the product are: placing the mixture into a forced air drying oven, and keeping the temperature for 12 hours at 60 ℃.
The method comprises the following specific operation steps: adding sodium hydroxide into mixed solution of ethylene glycol and water, then stirring uniformly, then sequentially adding diatomite and ferric nitrate to make the added ferric nitrate and NaOH react to generate Fe (OH) 3 Precipitating to the surface of diatomite; transferring the mixture into a PPL lining in a high-pressure reaction kettle, then putting the PPL lining into a blast drying oven, heating to 200 ℃, and keeping for 12 hours. After cooling to room temperature, washing with deionized water and ethanol for several times, and then washing and drying the product.
The photocatalyst performance was evaluated as H under light irradiation 2 O 2 Evaluation by degradation of tetracycline hydrochloride by Fenton-like.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1、M-SFS/α-Fe 2 O 3 the photocatalyst is a material which is low in cost and environment-friendly.
2、M-SFS/α-Fe 2 O 3 The synthesis method of the photocatalyst is that the photocatalyst is prepared in a mixed solution of ethanol and water by a high-temperature solvothermal method.
3、M-SFS/α-Fe 2 O 3 The photocatalyst is compared with nonmagnetic SFS/alpha-Fe 2 O 3 The photocatalyst not only has the advantage of easy recovery of magnetism, but also has greatly improved photocatalytic performance.
4. The novel magnetic M-SFS/alpha-Fe prepared by the invention 2 O 3 The photocatalyst has the characteristics of simple and convenient operation, few steps, low cost, environmental friendliness, obvious performance improvement, easiness in large-scale mass production and the like, and has good development prospect and industrial application potential.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample in example;
FIG. 2 is a graph showing the UV-visible diffuse reflectance absorption spectrum of the sample in the example;
FIG. 3 shows SFS/α -Fe in example 2 O 3 And M-SFS/alpha-Fe 2 O 3 A hysteresis loop spectrogram;
FIG. 4 shows M-SFS/α -Fe in example 2 O 3 (ii) a transmission electron microscopy spectrum;
FIG. 5 shows M-SFS/α -Fe in example 2 O 3 An X-ray photoelectron spectroscopy spectrum of (a);
FIG. 6 is a spectrum of the photo-Fenton degradation TC performance of the photocatalyst in the example.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
1) And (3) purifying diatomite: continuously stirring the diatomite in a 1.0mol/L dilute sulfuric acid solution for 6 hours, continuously washing the diatomite to be neutral by deionized water, drying the diatomite for 24 hours at the temperature of 60 ℃, and then reserving the diatomite for later use.
60mg of diatomaceous earth and 1.0g of NaOH were added to a mixture of 20mL of ethylene glycol and 10mL of ultrapure water, and the mixture was stirred for 1 hour.
2) Stirring the mixed solution obtained in step 1) continuously, and adding 1.2g of Fe (NO) 3 ) 3 ·9H 2 The powder of O was slowly added to the mixture obtained in step 1) and stirring was continued for 1 h.
3) Transferring the mixed liquid raw material obtained in the step 2) to a PPL lining in a high-pressure reaction kettle, then putting the PPL lining into a blast drying oven, heating to 180 ℃, and keeping for 12 hours. After cooling to room temperature, the mixture was washed several times with deionized water and ethanol. The yellow-green sample was dried in a forced air oven at 60 ℃ for 12h and collected to give the M-SFS/FO photocatalyst.
4) Measurement of photocatalytic performance: in a 100ml beaker, 30mg of photocatalyst was added to 50ml of a 20mg/L tetracycline hydrochloride (TC) solution. Before light, stir in dark for 30min to reach adsorption and desorption equilibrium. Then placing the mixed solution under a xenon lamp, taking 2.6ml of solution at regular intervals under the irradiation of visible light (lambda is more than or equal to 420nm), removing powder by using a filter head with the diameter of 0.22 mu m, and measuring the characteristic peak change of TC by using a UV-3600Plus Shimadzu ultraviolet visible spectrophotometer at the wavelength of 357nm to judge the concentration change of TC.
Comparative example 1
In NaOH aqueous solution, sequentially adding diatomite and ferric nitrate nonahydrate serving as silicon source and iron source into the solution, stirring uniformly, transferring into a PPL liner high-pressure reaction kettle, and preparing nonmagnetic SFS/alpha-Fe by hydrothermal method 2 O 3 A photocatalyst; then washed and dried. The conditions were the same as in example 1 except that ethylene glycol was not used in the comparative example.
Fig. 1 is an XRD spectrum of the photocatalyst. As can be seen from the figure, the SFS/alpha-Fe prepared 2 O 3 And M-SFS/alpha-Fe 2 O 3 The composite simultaneously shows SFS and alpha-Fe 2 O 3 Indicating successful preparation of SFS and alpha-Fe 2 O 3 The complex of (1). Due to M-SFS/alpha-Fe 2 O 3 Fe in composites 3 O 4 Is less and has poor crystallinity, and thus a diffraction peak thereof cannot be found in an XRD spectrum.
FIG. 2 is a graph of the UV-VIS diffuse reflectance spectrum of a photocatalyst. As can be seen from the figure, SFS/α -Fe 2 O 3 The light absorption range of photocatalysis is compared with that of alpha-Fe 2 O 3 A slight decrease in this indicates the presence of SFS in the complex species. And SFS/alpha-Fe 2 O 3 And M-SFS/alpha-Fe 2 O 3 The composites all showed good light absorption and compared to SFS/alpha-Fe 2 O 3 Photocatalytic, M-SFS/alpha-Fe 2 O 3 The light absorption range of the composite is larger due to the introduction of magnetic Fe 3 O 4 The result is. The light absorption range becomes larger meaning that more photoelectrons can be absorbed to improve the light utilization efficiency.
FIG. 3 is SFS/α -Fe 2 O 3 And M-SFS/alpha-Fe 2 O 3 Hysteresis curve spectrum ofFigure (a). To evaluate the magnetic behavior of the composite, SFS/α -Fe was tested at 300K 2 O 3 And M-SFS/alpha-Fe 2 O 3 The sample is subjected to magnetic measurements. SFS/alpha-Fe 2 O 3 The magnetic strength of (a) is very weak and almost negligible. At the same time, M-SFS/alpha-Fe 2 O 3 The saturation value (Ms) of magnetization can reach 20.3emu g -1 . This indicates that good magnetic properties can make the composite material easier to recycle.
FIG. 4 shows M-SFS/α -Fe 2 O 3 Transmission electron microscopy spectrogram of (1). It can be seen from the figure that the microtopography appears as an agglomerated nanosheet structure. Also, as can be seen from the figure, α -Fe 2 O 3 Has a lattice spacing of 0.220nm, corresponding to its (113) crystal plane. The lattice spacing of SFS is 0.290nm, corresponding to its (310) crystal plane, and 0.148nm corresponds to alpha-Fe 2 O 3 The (440) plane of (c). The result shows that the complex has SFS and alpha-Fe simultaneously 2 O 3 And Fe 3 O 4 Meanwhile, the HRTEM can show that the three are in close contact, so that the high-efficiency transmission of interface electrons is ensured, and the photocatalytic activity is promoted.
FIG. 5 shows M-SFS/α -Fe 2 O 3 X-ray photoelectron spectroscopy. XPS spectrum shows the existence of Na, Fe, Si, O and other elements, which indicates the existence of SFS in the compound. Meanwhile, the fine spectrogram of the Fe element is subjected to peak separation, and the analysis result shows that the Fe element is subjected to peak separation 2+ And Fe 3+ Also indicates the presence of Fe 3 O 4 The existence of the substance, and the result is consistent with the result of TEM image analysis.
Fig. 6 is a graph of the activity of the photocatalytic degradation TC of different photocatalysts. Under the irradiation condition of visible light (lambda is more than or equal to 420nm), using H 2 O 2 As an activator, 20mg/L of TC was subjected to photocatalytic degradation. From the figure, the self-degradation of TC and H only can be seen 2 O 2 In the presence of which conditions are negligible. SFS and alpha-Fe are added 2 O 3 The degradation rate of TC within 30min after the catalyst reaches 32.4 percent and 66.5 percent, and the degradation rate of SFS/alpha-Fe 2 O 3 The degradation rate of the compound is obviously improved to 84.34 percent, and magnetic Fe is further introduced 3 O 4 Formation of M-SFS/alpha-Fe 2 O 3 After the compound is compounded, the photocatalytic degradation efficiency of the compound on TC is further improved to 92.25 percent. In a word, the prepared M-SFS/FO composite photocatalyst not only realizes the obvious improvement of the photocatalytic performance, but also has the magnetic property and is more convenient to recycle, thereby having great advantage in the application of treating practical wastewater in the future.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any improvements and modifications made according to the spirit of the present invention are within the scope of the present invention.
Claims (9)
1. A preparation method of a magnetic sodium iron silicate/hematite composite photocatalyst is characterized by comprising the following steps:
firstly, adding NaOH into a mixed solution of ethylene glycol and water, sequentially adding diatomite and ferric nitrate nonahydrate, stirring uniformly, transferring into a PPL (polypropylene random copolymer) lined high-pressure reaction kettle, and preparing a magnetic M-SFS/alpha-Fe 2O3 photocatalyst by hydrothermal method; then washed and dried.
2. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst, as claimed in claim 1, wherein the mass ratio of the diatomite to the ferric nitrate nonahydrate is 1: 50-200.
3. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst as claimed in claim 1, wherein the concentration of sodium hydroxide in the mixed solution is 5-50 g/L.
4. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst according to claim 1, wherein the volume ratio of the ethylene glycol to the water is 3: (1-3).
5. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst as claimed in claim 1, wherein the hydrothermal condition is 180 ℃ and 200 ℃ for 10-20 h.
6. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst as claimed in claim 1, wherein the specific conditions for drying the product are as follows: and (5) placing the mixture into a forced air drying oven, and keeping the temperature for 12 hours at 60 ℃.
7. The preparation method of the magnetic sodium iron silicate/hematite composite photocatalyst, according to claim 1, is characterized by comprising the following specific operation steps: adding sodium hydroxide into mixed solution of ethylene glycol and water, then stirring uniformly, then sequentially adding diatomite and ferric nitrate to make the added ferric nitrate and NaOH react to generate Fe (OH) 3 Precipitating to the surface of diatomite; transferring the mixture into a PPL lining in a high-pressure reaction kettle, then putting the PPL lining into a blast drying oven, heating to 200 ℃, and keeping for 12 hours; after cooling to room temperature, washing for several times by deionized water and ethanol, and then washing and drying the product.
8. A magnetic sodium iron silicate/hematite composite photocatalyst prepared by the method of any one of claims 1 to 7.
9. Use of a magnetic sodium iron silicate/hematite composite photocatalyst prepared by the method of any one of claims 1 to 7 and prepared by the method of H 2 O 2 Tetracycline hydrochloride was degraded by a photo-Fenton-like reaction.
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