CN113697859A - Cladding hollow copper ferrite nanosphere material and preparation method and application thereof - Google Patents
Cladding hollow copper ferrite nanosphere material and preparation method and application thereof Download PDFInfo
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- CN113697859A CN113697859A CN202110968327.8A CN202110968327A CN113697859A CN 113697859 A CN113697859 A CN 113697859A CN 202110968327 A CN202110968327 A CN 202110968327A CN 113697859 A CN113697859 A CN 113697859A
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- China
- Prior art keywords
- hollow copper
- copper ferrite
- nanosphere
- nanosphere material
- water
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 239000002077 nanosphere Substances 0.000 title claims abstract description 53
- 238000005253 cladding Methods 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960004306 sulfadiazine Drugs 0.000 claims abstract description 31
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- 238000000034 method Methods 0.000 claims abstract description 20
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical group [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 8
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims abstract description 8
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- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical group [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 23
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- 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 description 2
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
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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
-
- B01J35/23—
-
- B01J35/615—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a cladding hollow copper ferrite nanosphere material and a preparation method and application thereof, wherein the cladding hollow CuFe nanosphere material2O4The nanosphere material is prepared by taking gamma-cyclodextrin with high solubility and rigid structure as a carbon source through a solvothermal method and further calcining. The invention also discloses the application of the material as a catalyst in removing antibiotics in water, the oxidant is selected from peroxymonosulfate, and test results show that the material has catalytic activityHigh stability, and can effectively improve the degradation efficiency of antibiotic Sulfadiazine (SD) in water when being used as a catalyst for activating PMS. In addition, the material has little transition metal dissolution in application, is environment-friendly and cannot cause secondary pollution; the process of degrading SD can be carried out at normal temperature and normal pressure without adding any energy, the pH application range is wide, the degradation efficiency is high, and the operation is simple, so the method has a higher application prospect in the field of advanced treatment of organic pollutants in water bodies.
Description
Technical Field
The invention belongs to the technical field of degradation of new environmental pollutants, and particularly relates to a cladding hollow copper ferrite nanosphere material as well as a preparation method and application thereof.
Background
Antibiotics are a class of secondary metabolites with anti-pathogen or other activities produced by microorganisms or higher animals and plants in the life process, and can interfere with other chemical substances with the development function of living cells. The antibiotics commonly used in clinic are extracts from microbial culture solutions and chemically synthesized or semi-synthesized compounds. Antibiotics have been widely used in clinical medicine and animal husbandry for the time period when antibiotics were discovered to date. Abuse of antibiotics in human daily activities easily produces "superbacteria". The hazards of abuse of antibiotics include, among others: the generation of toxic effects, long-term or over standard abuse of veterinary drugs, especially antibiotics and hormones as feed additives, and the harm of the feed additives not only reduces the quality of animal products and causes great economic loss, but also harms human health, such as 'grey infant syndrome' reaction; destruction of the micro-ecological environment and secondary infection: the long-term use of extensive antibiotics causes the dysbacteriosis of organism colony groups, the balance of microorganisms is destroyed, and potential harmful bacteria in vivo propagate in large quantities to form endogenous infection, namely 'secondary infection'; allergies and allergies: frequently eating animal food containing penicillin, tetracycline, sulfonamides and some aminoglycoside antibiotics residues can cause allergic reaction of susceptible individuals, and serious individuals can cause rash, dyspnea, acute angioedema, shock and even death; produce the effect of three causes: some antibiotics have teratogenic, carcinogenic and mutagenic effects, and human beings mainly take animal foods such as meat, milk and the like to cause pathological changes, such as chloramphenicol which can damage the hematopoietic function of human liver and bone marrow, and cause aplastic anemia and thrombocytopenia. The long-term accumulation of antibiotics in water bodies can cause the appearance of microbial drug resistance and resistance genes in the water bodies or soil, and form potential health risks for the environment and human health.
In recent years, studies have been madeIndicating that advanced oxidation processes are considered to be an irreplaceable and scientifically effective method for eliminating persistent and non-biodegradable antibiotics from water. In view of the advantages of excellent catalytic activity and a widely applicable pH range, the advanced oxidation process based on activated peroxymonosulfate is favored by most scholars. According to investigation, Potassium Monopersulfate (PMS) can generate sulfate radical (SO) under the activation of metal-based catalyst4 ·-2.5-3.1V), hydroxyl radical (. OH, 2.2-2.7V) and the like. Among the numerous activation methods, bimetallic ferrites (MFe) do not require additional external energy due to their metallic nature2O4Co, Cu, Mn, Ni, etc.) is one of the most preferred catalysts currently being used by researchers, and is widely used in the fields of sensors, lithium ion cathode materials, magnetic memories, catalytic oxidation, and the like. In most applications, Cu-based catalysts have catalytic efficiencies inferior to Co-based materials, but are limited to cobalt toxicity and are considered to be potential carcinogens and abandoned.
Due to the unique structure of the hollow sphere nano composite material, the hollow sphere nano composite material has wide application prospects in the aspects of catalysis, nano reactors, drug delivery vehicles, photonic devices, chemical sensors, biotechnology, energy conversion and storage systems and the like, and is widely concerned. For example, researchers have prepared tri-shell α -Fe by heterogeneous nucleation of ferric nitrate using carbonaceous microspheres as templates2O3Hollow microspheres and high capacity negative electrode materials for lithium ion batteries, the electrode performance being attributed to the large specific surface area and enhanced capacity of the multi-shelled hollow spheres, providing maximum lithium storage, while the porous thin shell promotes fast electrochemical kinetics and buffers mechanical stress; multi-shell heterostructure TiO prepared by researchers2/Fe2TiO5The hollow microsphere is used as a photo-anode material and shows excellent performance when being subjected to a hydrolytic photo-hydrolysis test, and the thickness of the hollow microsphere is up to 375 mu mol g-1·h-1The water-oxygen oxidation reaction rate and the extremely high stability (5 hours), the excellent performance of which is derived from a porous, hollow, thin-shelled, multi-shelled structure, which provides more reaction sites, stronger reflection and scattering power, and a self-supporting structure to support the internal shell and reduce light generationThe multi-shell hollow heterostructure has good light absorption and enhanced charge separation and transport characteristics, and has wide prospect for the solar water splitting technology.
In the methods reported above, most involve a multi-step templating process, the catalytic material adopts a relatively simple geometry, such as one component of a single shell sphere. Hollow spheres with high complexity, such as claddings or multi-layer hollow composite materials, are ideal choices for maximizing the structural advantages of expected catalytic activation performance.
In conclusion, the invention takes gamma-cyclodextrin with higher solubility and rigid structure as a carbon source to prepare the cladding CuFe by a solvothermal method and further calcination2O4Hollow microspheres served as catalysts for activating PMS, and their degradation studies were systematically performed on the typical antibiotic Sulfadiazine (SD) in water.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cladding hollow copper ferrite (CuFe)2O4) Nanosphere material, preparation method and application thereof, and cladding hollow CuFe2O4The nanosphere material is prepared by taking gamma-cyclodextrin with high solubility and structural rigidity as a carbon source through a solvothermal method and further calcining treatment, has high catalytic activity and good stability, and can effectively improve the degradation efficiency of antibiotics Sulfadiazine (SD) and the like in water as a catalyst for activating PMS.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a cladding hollow copper ferrite nanosphere material, which comprises the following steps:
(1) dissolving gamma-cyclodextrin, iron salt and copper salt in a solvent to obtain a reaction solution; transferring the reaction solution into a high-pressure reaction kettle for hydrothermal reaction, and after the reaction is finished, sequentially performing suction filtration, washing and drying on the obtained brown mixture to obtain a dry material; further, the iron salt is FeCl3·6H2O, the copper salt is CuCl2·2H2O; the solvent is BMixed solution of alcohol and deionized water according to the volume ratio of 1: 1; the temperature of the hydrothermal reaction is 165-175 ℃, and the time is 10-15 h.
(2) Grinding the dried material, calcining, and naturally cooling to room temperature to obtain the coated hollow copper ferrite nanosphere material (CuFe)2O4) (ii) a Furthermore, the temperature of the calcination treatment is 400-500 ℃, and the time is 1.6-2.5 h.
The invention also provides the application of the cladding hollow copper ferrite nanosphere material as a catalyst in removing antibiotics in water, which comprises the following steps: adding the cladding hollow copper ferrite nanosphere material and peroxymonosulfate into water containing antibiotics, carrying out degradation reaction under the stirring condition, and effectively degrading and removing the antibiotics in the water by using an oxidant peroxymonosulfate under the catalysis of the cladding hollow copper ferrite nanosphere material. Further preferably, the antibiotic is sulfadiazine; the peroxymonosulfate is potassium monopersulfate (KHSO)5·0.5KHSO4·0.5K2SO4PMS); the adding amount of the cladding hollow copper ferrite nanosphere material is 0.05-0.5 g/L; the concentration of the PMS in water is 0.1-1.0 mM; the pH of the water containing the antibiotic is 3.5-9.0.
The invention has the beneficial effects that:
(1) the cladding hollow CuFe prepared by the invention2O4The nanosphere material has high catalytic activity and good stability, can quickly adsorb an oxidant on the solid phase surface by taking the nanosphere material as an activator of peroxymonosulfate, generates active substances such as free radicals through the activation of exposed metal ions on the surface, and has higher activation efficiency on target antibiotics than that of a solid spherical catalyst.
(2) The cladding hollow CuFe prepared by the invention2O4The nanosphere material is used as a catalyst in the application of removing antibiotics in water, has a wide applicable pH range, can be directly treated in wastewater with the pH of 3.5-9.0, reduces the additional acid-base adding cost, has high degradation efficiency on antibiotic residues, has little metal precipitation, is efficient and stable, can be recycled, and has good practical application value. Under the mild conditions of the experiment, the reaction solution,the removal efficiency of the antibiotics can be up to more than 94% in a short time.
Drawings
FIG. 1 is a schematic representation of the clad hollow CuFe prepared in example 12O4SEM image of nanosphere material;
FIG. 2 is a schematic representation of the clad hollow CuFe prepared in example 12O4TEM images of nanosphere materials;
FIG. 3 is a schematic representation of the clad hollow CuFe prepared in example 12O4The adsorption and desorption curve and the aperture distribution diagram of the nanosphere material;
FIG. 4 is a schematic representation of the clad hollow CuFe prepared in example 12O4XRD spectrogram of the nanosphere material;
FIG. 5 is a schematic representation of the clad hollow CuFe prepared in example 12O4Cu2p and Fe 2pXPS spectra of the nanosphere material;
FIG. 6 is a schematic representation of the clad hollow CuFe prepared in example 12O4Peak spectrograms of Cu2p and Fe2p of the nanosphere material;
FIG. 7 is the hollow CuFe of the coating layer in example 22O4PMS and CuFe2O4PMS influences the SD degradation rate and primary dynamics fitting;
FIG. 8 is hollow CuFe as a coating layer in example 22O4The influence of the addition amount on the SD degradation rate and the first-order kinetic fitting of the SD degradation rate;
FIG. 9 is the effect of PMS concentration on SD degradation rate in example 2;
FIG. 10 shows the effect of pH on SD degradation rate and the system recycling experiment in example 2.
Detailed Description
The invention is further described with reference to the following figures and examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and suppliers of experimental drugs and reagents used in the following examples are shown in table 1 below:
table 1 main chemical and reagent lists and their suppliers.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1
A preparation method of a cladding hollow copper ferrite nanosphere material comprises the following steps:
(1) 6.0g of gamma-cyclodextrin (gamma-CD), 2.0g of FeCl3·6H2O and 1.0g CuCl2·2H2Adding O into the mixture in a volume ratio of 1:1, stirring vigorously until the mixture is dispersed uniformly, transferring the mixture into a sealed polytetrafluoroethylene reaction kettle, heating the mixture at 165 ℃ for 12 hours, centrifuging a brown product obtained by the reaction, alternately cleaning the brown product with deionized water and ethanol for 3 times, and drying the brown product in a drying oven at 60 ℃ for 24 hours to obtain a dried material;
(2) grinding the dried material, placing in a muffle furnace, heating to 500 deg.C at a speed of 1 deg.C/min, maintaining for 3 hr, and naturally cooling to obtain cladding hollow CuFe2O4A nanosphere material.
The above cladding hollow CuFe2O4The principle of forming nanosphere materials is based on the adsorption characteristics of carbon source gamma-cyclodextrin and hydrated metal ions. For the same metal surface, the ethanol enhances the wettability by destroying the hydrogen bonds and cohesion among water molecules, so that the solution further permeates into the carbon spheres and deposits more metal cations. Therefore, ethanol is selected as an additive to adsorb the concentration of iron ions and copper ions deep in the carbon microsphere template, and multiple separation of the shell and the interior is further completed through an annealing process.
For the clad hollow CuFe prepared in this example2O4The nanosphere material was subjected to structural analysis, and the results were as follows:
FIG. 1 is a cladding hollow CuFe2O4SEM image of nanosphere material, and annealed CuFe can be observed from FIG. 12O4The nanosphere material is spherical and porous on the surface, and a hollow layer in the inner space of the nanosphere material can be seen at the broken part, namely the nanosphere material is of a multilayer hollow structure. FIG. 2 is a cladding hollow CuFe2O4TEM image of the nanosphere material shows that after high-temperature calcination, a hollow microsphere structure with a cladding is obtained, which is consistent with the structure shown in SEM picture, wherein the number of the cladding layers is not uniform, thus being beneficial to the later degradation experiment.
FIG. 3 is a layer of hollow CuFe2O4The adsorption and desorption curve and the aperture distribution diagram of the nanosphere material. As can be seen from FIG. 3, the specific surface area of the material is as high as 182.98m2The surface porosity was also verified in terms of/g, with an average pore size of 9.61 nm.
Hollow CuFe of counter cladding2O4The crystal structure of the nanosphere material is studied, and the XRD pattern is shown in figure 4. Reference CuFe2O4The standard diffraction peak map (JCPDS 77-0010, Fd-3m) corresponds to the crystal faces with 2 theta characteristic peaks at 18.34 degrees, 30.18 degrees, 35.54 degrees, 43.20 degrees, 53.59 degrees, 57.14 degrees and 62.74 degrees to (111), (220), (311), (400), (422), (511) and (440), so that the prepared catalyst belongs to a cubic crystal structure.
FIG. 5 is a cladding hollow CuFe2O4Cu2p and Fe 2pXPS spectra of nanosphere material, as shown in a and b in FIG. 5, two spectra were observed at 954.0eV and 933.6eV, which are respectively Cu2p1/2And Cu2p3/2Intense peak signals of spin orbitals, Fe2p observed at 725.5eV and 712.0eV1/2And Fe2p3/2Orbital peak. Cubic CuFe2O4Is typically an "inverse" spinel ferrite, with Cu in the structure2+Occupying octahedral voids, Fe3+Distributed mainly among tetrahedral and octahedral voids. FIG. 6 is a cladding hollow CuFe2O4Cu2p and Fe2p peak spectra of the nanosphere material, as shown in a picture in figure 6, Cu2p3/2Photoelectron peak binding energies at 933.30eV and 934.80eVCu (I) in tetrahedral voids and Cu (II) in octahedral voids, wherein the Cu (I) distribution area is large. Cu2p1/2The main peaks with the photoelectron peaks of 953.0eV and 954.32eV belong to Cu (I) occupying tetrahedral voids and Cu (II) occupying octahedral voids, and the characteristic satellite peaks of Cu (II) are observed at 941.85eV and 962.11 eV. As can be seen from the b plot in fig. 6, the Fe2p spectrum of the sample was fitted to a collection of six peaks, with the main peaks at binding energies 710.79eV and 724.09eV being attributed to Fe (ii), while Fe (iii) is the main peak at binding energies 713.5eV and 726.01eV, with the tetrahedral void occupying the cubic crystal being the characteristic satellite peak of Fe (iii) at 718.68 eV. Comprehensive CuFe2O4The XPS spectra show that there are several chemical states of copper and iron in the catalyst structure, which greatly facilitate activation of PMS in solution.
Example 2
Clad hollow CuFe prepared as in example 12O4The nanosphere material is used as a catalyst for removing the antibiotic SD in water, and comprises the following steps:
20mg/L SD and 0.5mM PMS were added to 100mL Erlenmeyer flasks, respectively, the pH of the solution was adjusted to 6.5, and then 0.2g/L C was added to coat the hollow CuFe2O4The nanosphere material was added and 1mL of the solution was removed after a time interval and immediately quenched with 1mL of methanol and filtered through a 0.22 μm aqueous filter to determine its concentration. Respectively researching the cladding hollow CuFe under the condition of controlling other conditions to be unchanged2O4The nano-sphere material is added in a concentration range of 0.05-0.5g/L, PMS mM and the experimental pH is controlled between 3.5-9.0. In the cyclic degradation experiment, the catalyst was recovered after each run was completed, washed with water and ethanol, and dried at 60 ℃. All experiments were also wrapped in tinfoil to avoid the effects of light.
All test data in the SD degradation experiments are the average of three tests. Carrying out quasi-first-order dynamics and quasi-second-order dynamics model fitting analysis on degradation dynamics behaviors by using a formula 1 and a formula 2:
Ct/C0＝exp(·k1t) (1)
l/Ct-1/C0＝k2t (2)
wherein: c0As initial concentration, CtIs CuFe2O4Concentration of SD (mg/g) in PMS at t min. k is a radical of1And k2(g/mg. min.) are the quasi-first order kinetic and quasi-second order kinetic rate constants.
Analytical method
The wavelength λ max of the ultraviolet absorption peak of SD was determined to be 264nm by ultraviolet-visible spectrophotometer calibration. And (4) calibrating and detecting the real-time concentration of the target antibiotic by using a liquid chromatograph. Wherein, the chromatography uses Agilent C18 column (4.6 × 250mm, 5 μm), the detection wavelength is 264nm, the flow rate is 0.5mL/min, the sample injection volume is 20 μ L, the temperature of the column incubator is set at 30 ℃, and the peak time of the experiment detection is 12 min. Wherein, the mobile phase of chromatographic detection is V, V is 60: 40 of a methanolic organic phase and 0.1% aqueous methanol. Isocratic elution, flow rate: 0.5mL/min, column oven: 30 ℃, injection volume: 5 μ L.
Analysis of results
CuFe2O4And the influence of the feed ratio and PMS concentration on the degradation performance:
generally, the degradation removal rate of SD is affected by many experimental factors at the same time. In FIG. 7, diagram a and diagram b respectively depict PMS and CuFe catalyst2O4And the influence of the common system on the degradation performance of SD and the dynamic straight line fitting of the SD. The experiment shows that the catalyst CuFe2O4The addition of (A) greatly improves the single PMS and CuFe2O4The degradation efficiency of SD is improved, and the degradation process conforms to the quasi-first-order kinetics. Meanwhile, in the analysis of the influence of the catalyst adding amount and the oxidant PMS concentration (as shown in figures 8 and 9), consistent with most research data, as the catalyst feeding amount is increased from 0.05 g/L to 0.5g/L, the PMS concentration is increased from 0.1mM to 1.0mM, the degradation rate of SD is obviously increased, and the degradation rate is stable at last.
Mineralization of SD and catalyst recycle experiments:
initial concentration and solution of contaminants in contaminant removal systemThe influence of pH on its own degradation is very significant. The effect of SD degradation due to the difference in initial pH was observed as graph a in fig. 10. The SD degradation efficiency appeared to be optimal around pH 5.0, 6.5 and 7.0 as the pH increased from 3.5 to 9.0. When the initial pH of the solution was adjusted to 3.5, the degradation efficiency decreased from 94% to around 79% at 120 minutes, probably due to the SO in the PMS fraction under acidic conditions4 2-Is present in a reduced active fraction. Also, as the pH increased from 7.0 to 9.0, the degradation efficiency decreased to around 81%, due to deprotonation of PMS under more basic conditions, resulting in lower efficiency of the active species produced. Therefore, acidic and alkaline environments have influence on the degradation SD of PMS activated by the catalyst, so that longer time may be required for full reaction to achieve ideal removal efficiency in the wastewater treatment process with larger pH value. In the neutral range (pH 5.0-7.0), the degradation condition of SD shows a good phenomenon, which provides certain advantages for the application of the catalyst in a neutral actual water sample in the future.
In the practical application of water environment treatment, the long-term stable use of the catalyst is particularly important. Thus the experiment was performed 6 cycles of degradation experiments (see figure 10). Experiments show that the degradation efficiency of the antibiotic SD is almost unchanged in the first three use processes, but the degradation effect is obviously reduced in the fourth cycle experiment. The phenomenon is mainly caused by the reduction of active sites, the loss of metal ions and the incomplete elution of pollutants caused by the factors of insufficient cleaning of the catalyst in the early use and circulation processes.
The invention realizes cladding hollow CuFe by changing the components of the solvent2O4And (5) constructing the internal structure of the microsphere. The CuFe is shown to be more than the CuFe reported in the past due to the unique porous hollow structure2O4The nanocomposite material has significantly enhanced catalytic activity. The cladding hollow structure not only improves the utilization rate of active sites of the catalyst, but also provides a more active metal surface for the catalytic oxidation process, thereby accelerating and increasing the activation process of PMS. In the presence of CuFe2O4In PMS degradation systemWithin 2 hours, the SD degradation efficiency reaches 94 percent, and certain degradation capability is maintained in multiple times of cyclic degradation. In conclusion, the obtained clad hollow CuFe2O4The microspheres are a potential advantageous material in the application of degrading and removing the antibiotic SD residues in the water body.
The foregoing is a more detailed description of the invention, taken in conjunction with specific preferred embodiments thereof, and it is not intended to limit the invention to the particular forms set forth herein. Numerous and reasonably equivalent modifications will occur to those skilled in the art to which the present invention pertains without departing from the spirit of the invention, and the scope of the patent protection afforded by the claims appended hereto should be considered as limited solely by the appended claims.
Claims (9)
1. A preparation method of a cladding hollow copper ferrite nanosphere material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving gamma-cyclodextrin, iron salt and copper salt in a solvent to obtain a reaction solution; transferring the reaction solution into a high-pressure reaction kettle for hydrothermal reaction, and after the reaction is finished, sequentially performing suction filtration, washing and drying on the obtained brown mixture to obtain a dry material;
(2) and grinding the dried material, calcining, and naturally cooling to room temperature to obtain the cladding hollow copper ferrite nanosphere material.
2. The preparation method of the clad hollow copper ferrite nanosphere material according to claim 1, wherein the method comprises the following steps: in the step (1), the ferric salt is FeCl3·6H2O, the copper salt is CuCl2·2H2O。
3. The preparation method of the clad hollow copper ferrite nanosphere material according to claim 1, wherein the method comprises the following steps: in the step (1), the solvent is a mixed solution composed of ethanol and deionized water.
4. The method for preparing the coated hollow copper ferrite nanosphere material according to claim 3, wherein the method comprises the following steps: in the step (1), the volume ratio of the ethanol to the deionized water is 1: 1.
5. the preparation method of the clad hollow copper ferrite nanosphere material according to claim 1, wherein the method comprises the following steps: in the step (1), the temperature of the hydrothermal reaction is 165-175 ℃, and the time is 10-15 h.
6. The preparation method of the clad hollow copper ferrite nanosphere material according to claim 1, wherein the method comprises the following steps: in the step (2), the calcining treatment temperature is 400-500 ℃ and the time is 1.6-2.5 h.
7. The cladding hollow copper ferrite nanosphere material is characterized in that: the coated hollow copper ferrite nanosphere material is prepared by the preparation method of any one of claims 1-6.
8. The coated hollow copper ferrite nanosphere material of claim 7 applied as a catalyst for removing antibiotics in water, wherein: the method comprises the following steps: adding the cladding hollow copper ferrite nanosphere material and peroxymonosulfate into water containing antibiotics, carrying out degradation reaction under the stirring condition, and effectively degrading and removing the antibiotics in the water by the peroxymonosulfate under the catalysis of the cladding hollow copper ferrite nanosphere material.
9. The coated hollow copper ferrite nanosphere material of claim 8 applied as catalyst for removing antibiotics in water, wherein: the antibiotic is sulfadiazine; the peroxymonosulfate is potassium monopersulfate; the adding amount of the cladding hollow copper ferrite nanosphere material is 0.05-0.5 g/L; the concentration of the potassium monopersulfate in the water is 0.1-1.0 mM; the pH of the water containing the antibiotic is 3.5-9.0.
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