CN117324015B - FeO (FeO)xSeyPreparation of nano wall catalytic material and application of nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics - Google Patents
FeO (FeO)xSeyPreparation of nano wall catalytic material and application of nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 42
- 230000015556 catabolic process Effects 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 12
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 11
- 229940124307 fluoroquinolone Drugs 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
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- 238000003756 stirring Methods 0.000 claims description 17
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 63
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 4
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- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 1
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
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- 229960002549 enoxacin Drugs 0.000 description 1
- IDYZIJYBMGIQMJ-UHFFFAOYSA-N enoxacin Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 IDYZIJYBMGIQMJ-UHFFFAOYSA-N 0.000 description 1
- 229960000740 enrofloxacin Drugs 0.000 description 1
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- 239000013384 organic framework Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229960000625 oxytetracycline Drugs 0.000 description 1
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
- 235000019366 oxytetracycline Nutrition 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- UHKHUAHIAZQAED-UHFFFAOYSA-N phthalocyaninatoiron Chemical compound [Fe].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 UHKHUAHIAZQAED-UHFFFAOYSA-N 0.000 description 1
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- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- C02F2101/36—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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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Abstract
Preparation of FeO xSey nano wall catalytic material and application thereof in photo-Fenton degradation of fluoroquinolone antibiotics. The Se-doped ferric oxide nanowall and the modified g-C 3N4 composite heterojunction catalytic material are developed by combining a supermolecule prepolymerization method, a solvothermal method and a calcination etching method. The g-C 3N4 is regulated and controlled by supermolecule prepolymerization to form a porous microstructure, an iron oxide nano wall is constructed on the surface of the porous microstructure in situ, a stable interface electric field is constructed, se is introduced into an iron oxide lattice structure by utilizing a calcination etching process, the coordination environment of Fe is regulated and controlled, and the adsorption performance of the Fe on H 2O2 is improved. Under the condition of visible light, the FOS/CN surface can form an effective Fe 2+ and Fe 3+ circulating system, and the reaction energy barrier for converting H 2O2 into OH can be effectively reduced. The degradation rate of the heterojunction catalytic material prepared by the invention to FQs series antibiotics can reach more than 95% after the photoFenton reaction is carried out for 10 min.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, relates to the technical research of preparation of FeO xSey nano-sheets and modified graphite phase carbon nitride heterojunction catalytic materials, and particularly relates to innovation of a method for degrading fluoroquinolone antibiotics by activating hydrogen peroxide under the condition of visible light by using the material.
Background
Fluoroquinolone antibiotics (fluoroquinolones, FQs) belong to the third class of antibiotics and are synthetic broad-spectrum antibacterial agents. Fluoroquinolone antibiotics are widely used in daily life and occupy 17% of the market quota worldwide due to their wide variety and broad spectrum antibacterial properties. The large and frequent use has led to FQs being ubiquitous in environmental bodies of water. Along with the continuous migration and transformation of the environment, FQs entering the water body can generate some intermediates with stronger toxicity, which can cause potential threat to ecological safety and human health. FQs antibiotics are stable in properties and have broad-spectrum antibacterial properties, so that the biological method of the traditional sewage treatment plant is difficult to realize effective removal. The research on the related high-efficiency degradation method and degradation mechanism is carried out on the pollutants, and the method has important practical significance for protecting the safety of water environment and the ecological balance of water.
The photocatalysis has the advantages of mild reaction condition, low energy consumption, higher catalytic reaction efficiency, no toxicity of the generated product and the like. However, photocatalysis has the defects of slow catalysis rate and low mineralization rate. During the photocatalytic process, hydrogen peroxide (H 2O2) is added, and H 2O2 is activated by photoexcitation and the action of a catalyst to generate hydroxyl radicals (. OH) of active species with strong oxidizing property. OH is a non-selective strong oxidizer that can effectively degrade a variety of refractory organic contaminants in water. For any catalytic reaction, the catalytic material plays an important role. Graphite phase carbon nitride (g-C 3N4) is one of the commonly used photocatalytic materials. Since 2009 Wang et al 'Amal-free polymeric photocatalyst for hydrogen production from water under visible light' uses the material as a metal-free photocatalytic material with stable performance for water decomposition, g-C 3N4 has been widely focused in the field of photocatalysis, but the application and development of the material still face the restriction of the problems of higher photo-generated electron-hole recombination rate, poor incident light capturing capability and the like. Aiming at the problems, the prior improvement measures comprise morphology modification, heterogeneous doping, composite heterojunction construction and the like. However, a single modification method still cannot effectively achieve efficient carrier migration and conversion. Meanwhile, the main active oxidation species generated by photocatalysis are superoxide radicals with negative charges, so that the active oxidation species have strong selectivity on degradation of organic pollutants and insufficient mineralization capability. Based on the above problems, researches on Fe-based complexes as photo-Fenton catalysts are paid attention to, and the cyclic conversion of Fe 2+/Fe3+ is promoted in article "Boosting photo-Fenton process enabled by ligand-to-cluster charge transfer excitations in iron-based metal organic framework"、"Graphite carbon nitride coupled with high-dispersed iron(II)phthalocyanine for efficient oxytetracycline degradation under photo-Fenton process:performance and mechanism" by constructing an iron-based organic framework structure, introducing an electron donor, and the like, respectively. Although the iron recycling can be promoted to a certain extent, the conversion efficiency of the catalytic material to H 2O2 can be improved, the light utilization rate of the material can be widened when the surface active sites of the material are increased, and the space still improved in the light-induced H 2O2 conversion can be promoted.
Therefore, the modified g-C 3N4 with the porous structure is selected as the substrate, the FeO xSey nano wall is prepared in situ in the hole wall to form a heterojunction catalytic material, and the porous structure on the surface of the substrate is utilized to maintain the stability of the FeO xSey nano wall; the mass transfer process between the pollutant and the catalytic material can be effectively enhanced by the larger specific surface area, and the spectrum utilization rate and the utilization range of the material are expanded; the interface electric field between the substrate and the FeO xSey nanometer wall can provide an electron directional migration channel, so that the migration and conversion capability of the photogenerated carriers are improved; in addition, the Se doping can effectively regulate and control the Fe coordination environment and the lattice structure, improve the adsorption and catalytic performance of the Fe coordination environment and the lattice structure on H 2O2, and simultaneously form a Fe 2+ and Fe 3+ circulating system on the surface of the FeO xSey nano wall under the effect of photo-generated electrons, so that the conversion process of H 2O2 to OH can be effectively catalyzed, and the aim of photo-Fenton degradation of FQs in water is fulfilled.
Disclosure of Invention
The invention provides a preparation method of a Se-doped ferric oxide (FeO xSey) nano wall and modified g-C 3N4 composite heterojunction catalytic material, and FQs is degraded by Yu Guangfen tons. The porous microstructure is formed by regulating g-C 3N4 through supermolecule prepolymerization, an iron oxide nano wall is constructed on the surface of the porous microstructure in situ, se is introduced into an iron oxide lattice structure through a calcining process, and a FeO xSey nano wall load modified g-C 3N4 heterojunction material (FOS/CN) is formed. Under the condition of visible light, the surface of FOS/CN can form a Fe 2+ and Fe 3+ circulating system, so that the reaction energy barrier for converting H 2O2 into OH can be effectively reduced, and the aim of efficiently degrading FQs in water by photo Fenton is fulfilled.
The technical scheme of the invention is as follows:
A preparation method of a FeO xSey nanometer wall catalytic material comprises the following steps:
Step 1: adding melamine, cyanuric acid and uramicin into a methanol solution, wherein the adding mass ratio of the melamine to the cyanuric acid is 3:1-1:2, the adding mass ratio of the melamine to the uramicin is 10:1-50:1, and stirring for 30-240min, wherein the concentration of the melamine is 25-50mg/mL; drying the obtained mixed solution in an oven at 40-50 ℃, grinding uniformly in a mortar, loading into a porcelain boat, calcining in a tubular furnace under the atmosphere of N 2 at the heating rate of 1-3 ℃/min, the reaction temperature of 400-600 ℃ and the reaction time of 2-4h, taking out the solid after the reaction, alternately cleaning the solid with deionized water and ethanol for 2 times, and drying in the oven at 60 ℃ to obtain yellow solid which is modified g-C 3N4;
Step 2: uniformly grinding the modified g-C 3N4 prepared in the step 1, putting the ground modified g-C 3N4 into a polytetrafluoroethylene lining filled with an ethylene glycol solution, and stirring for 30min, wherein the adding amount of the modified g-C 3N4 is 4-20mg/mL; adding ferrous sulfate after stirring uniformly, continuing stirring for 30min, wherein the adding mass ratio of the modified g-C 3N4 to the ferrous sulfate is 4:1-20:1, introducing N 2 into the glycol solution during stirring, then placing the polytetrafluoroethylene lining into a stainless steel reaction kettle for sealing, carrying out solvothermal reaction for 10-16h at the reaction temperature of 160-220 ℃, separating solids in a suction filtration mode after the reaction is finished, cleaning for three times by ethanol and deionized water respectively, placing into a vacuum drying box, and drying for 24h at the temperature of 40 ℃ to obtain yellowish green powder FeO x/CN;
Step 3: uniformly mixing the FeO x/CN and the Se simple substance obtained in the step 2, and then placing the mixture into a porcelain boat, wherein the mass ratio of FeOx/CN to Se is 5:1-1:2; calcining in a tube furnace under the atmosphere of N 2 at the reaction temperature of 250-400 ℃ for 1-4h to obtain the FeO xSey/g-C3N4 (FOS/CN) heterojunction catalytic material, namely the FeO xSey nano-wall catalytic material.
Application of FeO xSey nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics, wherein FeO xSey nano wall catalytic material is used as a catalyst for degradation of TBBPA; under the condition of visible light, the reaction temperature is 24-26 ℃, the wastewater with the concentration of 1-10mg/L FQs is used as a target, the reaction time is 20min, and the FQs degradation rate can reach more than 98%.
The invention has the beneficial effects that: in the method, the composite heterojunction catalytic material (FOS/CN) of the Se-doped ferric oxide nano wall and the modified g-C 3N4 is used for realizing the efficient degradation of photoFenton under the condition of visible light and mineralizing FQs in water for the first time. The preparation method comprises the steps of firstly forming a macromolecule prepolymer with an ordered structure from a precursor for preparing graphite-phase carbon nitride by a supermolecule prepolymerization method in the step 1, and then forming a modified g-C 3N4 with a vacancy structure and S doping by calcining, polycondensing and rearranging, wherein the microscopic morphology is porous coral reef-shaped, and compared with the g-C 3N4 prepared by the traditional method, the modified g-C 3N4 prepared in the patent can effectively inhibit pi-pi stacking phenomenon, construct a three-dimensional interpenetrating network structure, increase the specific surface area of materials, provide an effective loading environment for the subsequent heterojunction preparation, and strengthen the capturing capability of the material to photon-generated carriers due to N defects and S doping in the structure, thereby improving the separation capability of carriers. Then, taking the modified g-C 3N4 as a substrate, loading FeO x nano walls on the surface of a porous substrate by a solvothermal method, introducing Se simple substance as a precursor, and calcining to prepare the FOS/CN heterojunction catalytic material. In the FOS/CN heterojunction material, the Se-doped ferric oxide nanowall structure (shown in figures 1 and 2) belongs to a semiconductor material, has good light response and conductivity, and a large amount of Fe 2+ exists in the structure, so that Fenton reaction is promoted; meanwhile, the doping of Se can effectively regulate and control the coordination environment and lattice structure of Fe, the adsorption performance of Fe sites on H 2O2 molecules can be effectively improved by utilizing an asymmetric coordination structure, and the reaction energy barrier of H 2O2 conversion to OH in the Fenton reaction process can be obviously reduced. The modified g-C 3N4 can effectively increase the mobility of carriers, and an interfacial directional electron transfer channel between interfaces can be constructed by utilizing an interfacial electric field between the modified g-C 3N4 and the Se-doped ferric oxide nanowall, so that photo-generated electrons can be quickly transferred to the surface of FeO xSey, further a Fe 3+ and Fe 2+ circulating system is formed, and the Fenton reaction is enhanced. Therefore, the material can realize the efficient degradation FQs of the photo Fenton under the condition of visible light.
Drawings
FIG. 1 is an SEM of FeOx/CN-1.
FIG. 2 is a SEM of the presence of FeO xSey characteristic lattice fringes in the HRTEM of FeOx/CN-1.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the technical scheme and the accompanying drawings.
Example 1
The preparation method of the FOS/CN heterojunction catalytic material comprises the following steps:
5g of melamine, 3g of cyanuric acid and 0.5g of uramicin were dispersed in 100mL of methanol and stirred for 120min. And (3) drying the uniformly stirred mixed solution in a blast oven at 60 ℃, grinding the dried solid in a mortar uniformly, putting the ground solid in a porcelain boat, calcining the ground solid in a tube furnace, protecting the dried solid by using N 2, reacting at 550 ℃ for 4 hours, taking out the solid after the reaction is finished, alternately cleaning the solid with deionized water and ethanol for 2 times, and putting the solid in the oven at 60 ℃ for drying to obtain the yellow solid which is modified g-C 3N4.
A series of modified g-C 3N4 (designated CN-400, CN-450, CN-500, CN-550 and CN-600) were prepared by selecting the calcination temperatures of 400, 450, 500 and 600. The influence mechanism of the preparation conditions on the modified g-C 3N4 structure and morphology is examined by structural characterization means such as a transmission electron microscope, an X-ray photoelectron spectrum, a Fourier transform infrared spectrum, an electron spin resonance spectrum and the like, and the result shows that the holes appearing on the surface of the modified g-C 3N4 structure are gradually increased along with the increase of the temperature, the agglomeration phenomenon is also gradually reduced, and the whole coral reef structure is presented, so that the specific surface area and the light utilization rate are increased. When the temperature exceeds 600 ℃, the product is substantially completely decomposed, and only a small amount of black carbon residue is present. The structural characterization result shows that CN-550 has the largest specific surface area, the highest doping amount of S and the largest N defect type and amount, so that the CN-550 is used as a substrate of a heterojunction catalytic material.
Grinding CN-550 uniformly, putting into a polytetrafluoroethylene lining filled with glycol solution, and stirring for 30min, wherein the adding amount of modified g-C 3N4 is 10mg/mL; adding ferrous sulfate after stirring uniformly, continuing stirring for 30min, wherein the adding mass ratio of CN-550 to ferrous sulfate is 8:1, introducing N 2 into the glycol solution in the stirring process, then placing the polytetrafluoroethylene lining into a stainless steel reaction kettle for sealing, carrying out solvothermal reaction for 12h, separating solid in a suction filtration mode after the reaction at 200 ℃, washing with ethanol and deionized water for three times respectively, placing into a vacuum drying box, and drying at 40 ℃ for 24h to obtain yellowish green powder FeO x/CN.
Uniformly mixing FeO x/CN and Se simple substances, and then placing the mixture into a porcelain boat, wherein the mass ratio of FeO x/CN to Se is 5:1, 4:1, 3:1, 2:1, 1:1 and 1:2. Calcining in a tube furnace at a reaction temperature of 350 ℃ under an N 2 atmosphere for 2 hours to obtain a series of FOS/CN materials (named FeO x/CN-5、FeOx/CN-4、FeOx/CN-3、FeOx/CN-2、FeOx/CN-1 and FeO x/CN-0.5) for subsequent degradation performance comparison test.
Example 2
The method for degrading ciprofloxacin by photo Fenton comprises the following steps: 15mg of FOS/CN series catalytic material was weighed and dispersed into a photo Fenton reactor containing 100mL ciprofloxacin solution (10 mg/L CIP), respectively. Before degradation experiments, stirring for 30min under dark conditions to enable the catalytic material and CIP to reach adsorption saturation, adding 100 mu L of 30% H 2O2 solution into the solution, then carrying out photo Fenton degradation test under visible light conditions, reacting for 20min at the temperature of 25 ℃, taking the reaction solution once at intervals of 2min, filtering the taken reaction solution with a 0.22 mu m filter membrane, taking 1mL of the reaction solution, adding 50 mu L of methanol into the reaction solution to quench Fenton reaction to ensure the test accuracy, and obtaining the degradation rate after instrument test. After the reaction was completed for 20 minutes, 15mL of the reaction solution was collected, and after filtration with a 0.22 μm filter, the TOC removal rate during degradation was measured.
The CIP concentration is measured by ultra-high performance liquid chromatography, and the test result shows that the reaction is carried out for 20min, the degradation rate of the FOS/CN series catalytic materials to CIP can reach more than 98%, and the mineralization rate is more than 20%. The FOS/CN-1 can completely degrade CIP in the solution (the removal rate is 99.9 percent, the mineralization rate is 30 percent) after reacting for 10 minutes, and the degradation performance of the FOS/CN-1 is superior to that of the series of other materials, and the FOS/CN-1 is used as a subsequent performance comparison test material.
Example 3
Degradation FQs method: 15mg of FOS/CN-1 was weighed and separately dispersed into a photo Fenton reactor containing 100mL of various FQs solutions (10 mg/L, enoxacin, levofloxacin, moxifloxacin, enrofloxacin, ofloxacin). Before degradation experiments, stirring for 30min under dark conditions to enable the catalytic material and CIP to reach adsorption saturation, adding 100 mu L of 30% H 2O2 solution into the solution, then carrying out photo Fenton degradation test under visible light conditions, reacting for 20min at the temperature of 25 ℃, taking the reaction solution once at intervals of 2min, filtering the taken reaction solution with a 0.22 mu m filter membrane, taking 1mL of the reaction solution, adding 50 mu L of methanol into the reaction solution to quench Fenton reaction to ensure the test accuracy, and obtaining the degradation rate after instrument test. After the reaction was completed for 20 minutes, 15mL of the reaction solution was collected, and after filtration with a 0.22 μm filter, the TOC removal rate during degradation was measured.
The concentration of FQs is measured by ultra-high performance liquid chromatography, and the test result shows that the degradation rate of FQs series pollutants reaches more than 95% in the reaction for 10min, which shows that FOS/CN-1 has excellent photo Fenton degradation performance for FQs series pollutants.
Example 4
Test of the effect of ions and natural organics on the photoFenton degradation performance: the method comprises the steps of adding cations such as sodium ions (NaNO 3), calcium ions (Ca (NO 3)2), magnesium ions (Mg (NO 3)2) and iron ions (Fe (NO 3)3)), adding anions such as nitrate ions (NaNO 3), sulfate ions (Na 2SO4), chloride ions (NaCl) and bicarbonate radicals (Na 2CO3) into a photo-Fenton reactor containing 100mL of CIP solution (10 Mg/L) respectively with 15Mg of FOS/CN-1, stirring for 30min under dark conditions before degradation experiments, enabling a catalytic material and CIP to reach adsorption saturation, adding 100 mu L of 30% H 2O2 solution into the solution, then carrying out photo-Fenton degradation test under visible light conditions, taking the reaction solution once at a reaction time of 25+/-1 ℃ at intervals of 2min, filtering the taken reaction solution with a 0.22 mu m filter membrane, adding 50 mu L of methanol to quench the reaction to ensure the accuracy of the test, and obtaining the degradation efficiency of the CIP with NO addition of the CIP solution after instrument test, thereby comparing the degradation efficiency with the natural degradation efficiency of the CIP and the natural degradation efficiency of the CIP.
The test results show that after the anions and cations are added, the degradation efficiency of CIP does not change obviously, so that the addition of the anions and the cations has no obvious effect on the degradation of CIP by FOS/CN-1 photo Fenton, but the addition of natural organic matters can seriously influence the degradation of CIP, which is probably caused by the competition reaction of the natural organic matters and the CIP in the degradation process.
Claims (2)
1. A preparation method of a FeO xSey nanometer wall catalytic material is characterized by comprising the following steps:
Step 1: adding melamine, cyanuric acid and uramicin into a methanol solution, wherein the adding mass ratio of the melamine to the cyanuric acid is 3:1-1:2, the adding mass ratio of the melamine to the uramicin is 10:1-50:1, and stirring for 30-240 min, wherein the concentration of the melamine is 25-50 mg/mL; drying the obtained mixed solution in an oven at 40-50 ℃, grinding uniformly in a mortar, loading into a porcelain boat, calcining in a tubular furnace under the atmosphere of N 2 at the heating rate of 1-3 ℃/min, the reaction temperature of 400-600 ℃ and the reaction time of 2-4 h, taking out the solid after the reaction, alternately cleaning the solid with deionized water and ethanol for 2 times, and drying in the oven at 60 ℃ to obtain yellow solid which is modified g-C 3N4;
Step 2: uniformly grinding the modified g-C 3N4 prepared in the step 1, putting the ground modified g-C 3N4 into a polytetrafluoroethylene lining filled with an ethylene glycol solution, and stirring for 30 min, wherein the adding amount of the modified g-C 3N4 is 4-20 mg/mL; adding ferrous sulfate after stirring uniformly, continuing stirring for 30 min, wherein the adding mass ratio of the modified g-C 3N4 to the ferrous sulfate is 4:1-20:1, introducing N 2 into the glycol solution during stirring, then placing the polytetrafluoroethylene lining into a stainless steel reaction kettle for sealing, performing solvothermal reaction at the temperature of 160-220 ℃ at 10-16 h, separating solids in a suction filtration mode after the reaction is finished, cleaning for three times by ethanol and deionized water respectively, placing into a vacuum drying box, and drying for 24 h at the temperature of 40 ℃ to obtain yellowish green powder FeO x/CN;
Step 3: uniformly mixing the FeO x/CN and the Se simple substance obtained in the step 2, and then placing the mixture into a porcelain boat, wherein the mass ratio of FeOx/CN to Se is 5:1-1:2; calcining in a tube furnace under the atmosphere of N 2 at the reaction temperature of 250-400 ℃ for 1-4 h to obtain the FeO xSey/g-C3N4 heterojunction catalytic material, namely the FeO xSey nano wall catalytic material.
2. An application of the FeO xSey nano-wall catalytic material obtained by the preparation method of claim 1 in photo-Fenton degradation of fluoroquinolone antibiotics, wherein the FeO xSey nano-wall catalytic material is used as a catalyst for degradation of TBBPA; under the condition of visible light, the reaction temperature is 24-26 ℃, the wastewater with the concentration of 1-10 mg/L FQs is used as a target, the reaction time is 20min, and the FQs degradation rate can reach more than 98%.
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