CN114956194A - Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate - Google Patents
Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate Download PDFInfo
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- CN114956194A CN114956194A CN202210427751.6A CN202210427751A CN114956194A CN 114956194 A CN114956194 A CN 114956194A CN 202210427751 A CN202210427751 A CN 202210427751A CN 114956194 A CN114956194 A CN 114956194A
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- persulfate
- iron oxyhydroxide
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- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 title claims abstract description 38
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 26
- 230000015556 catabolic process Effects 0.000 title claims abstract description 24
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 18
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 17
- 239000004098 Tetracycline Substances 0.000 claims abstract description 21
- 229960002180 tetracycline Drugs 0.000 claims abstract description 21
- 229930101283 tetracycline Natural products 0.000 claims abstract description 21
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 21
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 22
- 230000003115 biocidal effect Effects 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960004887 ferric hydroxide Drugs 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012984 antibiotic solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 229910002588 FeOOH Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010042566 Superinfection Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 208000022531 anorexia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 206010061428 decreased appetite Diseases 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- 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
-
- B01J35/39—
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
The invention discloses iron oxyhydroxide and application thereof as a photocatalytic material to degrade antibiotics in cooperation with persulfate. The chemical general formula of the iron oxyhydroxide is FeOOH, the application of the combined action of the iron oxyhydroxide and persulfate in the photocatalytic degradation of tetracycline is disclosed, the reaction condition is mild, the tetracycline removal rate is high, and the material after catalytic degradation is easy to recycle.
Description
Technical Field
The invention relates to the field of photocatalytic degradation, in particular to iron oxyhydroxide and application thereof as a photocatalytic material to degrade antibiotics in cooperation with persulfate.
Background
Antibiotics are the most widely used class of drugs in recent years, but bring convenience and cause many problems. Only a small part of the biodegradable polysaccharide can be degraded after entering a human body, and the biodegradable polysaccharide is difficult to metabolize by self in the environment, so that the life health and the environmental safety of people are seriously harmed. The excessive use of antibiotics or the accumulation of antibiotics in the body can cause serious side effects, such as nausea, vomiting, anorexia, superinfection, influence on the growth of bones and teeth, and the like, and the harm to the environment is also serious.
At present, there are several methods for degrading antibiotic-type pollutants in water, including traditional chemical treatment, electrochemical method, microbial oxidation and photodegradation. However, the traditional chemical method can not effectively remove a large amount of tetracycline, and can introduce new pollutants, and the electrochemical method and other methods have high energy consumption. Compared with other methods, photocatalysis has the advantages of mild reaction conditions, simple equipment, less secondary pollution, utilization of sunlight as the only external energy input and the like, and is a promising pollution control technology.
Based on SO 4 · - The photocatalysis method is widely applied to degrading organic pollutants due to the advantages of strong oxidation performance, good oxidant stability, environmental protection, harmlessness and the like. SO (SO) 4 · - Persulfate salts can be generally activated and generated by light, microwaves, ultrasound, heat, transition metal ions, metal and metal-free catalysts, and the like. Among them, transition metal ions are easily activated without additional energy input, and have been widely studied. In systems based on transition metalsIron-based catalysts/persulfates differ by the chemical state of iron (Fe) 0 、Fe 2+ 、Fe 3+ ) It is a highly flexible system.
Therefore, the iron-based catalyst/persulfate system is coupled with photocatalysis to construct a multi-reaction coupled advanced oxidation system for efficiently degrading organic pollutants in water, which is a hot point of current research. Among iron-based catalysts, iron oxyhydroxides are attracting much attention due to environmental friendliness, relative stability, visible light response, strong corrosion resistance, and low cost. Therefore, the iron oxyhydroxide photocatalyst is successfully prepared, and a multi-reaction coupling type advanced oxidation system (photocatalysis + persulfate activation) is constructed by coupling persulfate.
Disclosure of Invention
The invention aims to provide iron oxyhydroxide and application thereof as a photocatalytic material to degrade antibiotics in cooperation with persulfate. The iron oxyhydroxide provided by the invention has smaller forbidden bandwidth and grain size, can generate an electron-hole pair with catalytic activity under proper illumination, and can capture the electron-hole pair and activate peroxydisulfate when antibiotic (tetracycline) is adsorbed on the surface of hydrotalcite, so that the tetracycline is degraded, and the aim of purifying wastewater is fulfilled.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of iron oxyhydroxide, which comprises the following steps: (1) dispersing CTAB (cetyl trimethyl ammonium bromide) in deionized water, and stirring for 30-60 min at room temperature until the solution becomes transparent to obtain a solution A; (2) FeCl is added 3 Dissolving the mixture in the solution A, and stirring the mixture for 30 to 60min at room temperature until a homogeneous solution is formed; (3) pouring the solution in the step (2) into a Teflon stainless steel high-pressure reaction kettle for hydrothermal reaction, and cooling to room temperature after the reaction is finished; (4) filtering under reduced pressure, washing the filter cake with ethanol and distilled water for 3 times respectively, and drying to obtain the iron oxyhydroxide.
Preferably, in the above method for preparing iron oxyhydroxide, the molar ratio of CTAB and ferric chloride in the steps (1) and (2) is 1: 1-1: 3, and the stepFeCl in step (2) 3 The concentration of (b) is 0.1 to 0.3 mol/L.
Preferably, in the preparation method of iron oxyhydroxide, the hydrothermal reaction temperature in the step (3) is 80-120 ℃, and the hydrothermal reaction time is 6-24 h.
Preferably, in the above method for preparing iron oxyhydroxide, the drying temperature in the step (4) is 50 to 60 ℃.
The invention also provides an application of the ferric hydroxide light synergistic activation persulfate in catalytic degradation of antibiotics, which comprises the following steps: (1) putting the provided iron oxyhydroxide and persulfate into an antibiotic aqueous solution together; (2) and (3) placing the mixed solution in the step (1) under a xenon lamp for irradiating for 0.5-2 h, and stirring to degrade the antibiotics.
Preferably, in the above application of the ferric hydroxide to the photocatalytic activation of the persulfate to degrade the antibiotic, the antibiotic is tetracycline.
Preferably, in the application of the iron oxyhydroxide photo-synergistic activation persulfate catalytic degradation antibiotic, the initial mass concentration of the tetracycline is 10-100 mg/L.
Preferably, in the above application of the iron oxyhydroxide photo-synergistic activation persulfate for catalytic degradation of antibiotics, the persulfate in the step (1) is sodium persulfate, potassium persulfate, sodium persulfate, or potassium persulfate.
Preferably, in the application of the ferric hydroxide photo-synergetic activation persulfate for catalytic degradation of the antibiotic, in the step (1), the ratio of the ferric hydroxide to the antibiotic solution is 10-100 mg:100mL, and the ratio of the persulfate to the antibiotic solution is 0.1-2 g:100 mL.
Preferably, in the application of the ferric hydroxide light synergistic activation persulfate to catalyze and degrade the antibiotic, visible light in a xenon lamp range of 400-800 nm is used in the step (2).
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the iron oxyhydroxide and the application of the iron oxyhydroxide in catalytic degradation of antibiotics by photo-synergetic activation persulfate have the advantages of easily obtained raw materials, lower cost, smaller forbidden bandwidth and smaller grain size of the prepared iron oxyhydroxide, mild antibiotic degradation reaction conditions, high degradation efficiency, capability of catalyzing the degradation of antibiotics under the sunlight condition, capability of obtaining good degradation efficiency without adding an extra electric field, remarkable degradation effect, easiness in recycling of the materials after catalytic degradation, capability of saving energy to the maximum extent while controlling environmental pollution, and no secondary pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an X-ray diffraction pattern of iron oxyhydroxide in example 1;
FIG. 2 is a graph of the degradation rate of the tetracycline of example 2;
FIG. 3 is a standard graph of the tetracycline of example 3.
Detailed Description
Example 1
Preparation of iron oxyhydroxide catalyst
1.4578g CTAB (4.0mmol) is weighed and dispersed in 30mL deionized water, and stirred for 30min at room temperature until the solution becomes transparent, and is marked as solution A; 1.0800g of FeCl were weighed separately 3 (6.7mmol) was dissolved in solution A and stirred for 30min until a homogeneous solution was formed; pouring the solution into a 50mL Teflon stainless steel high-pressure reaction kettle, and heating for 12h at 90 ℃; after the reaction is finished, the reaction kettle is cooled to room temperature. Filtering under reduced pressure, washing the filter cake with ethanol and distilled water for 3 times respectively, and drying at 60 ℃ for 12h to obtain the iron oxyhydroxide catalyst. The X-ray diffraction pattern (XRD) is shown in fig. 1.
Example 2
Photocatalytic experiment
The method is characterized in that simulated sunlight is adopted to degrade tetracycline to serve as a model reaction, and an ultraviolet-visible spectrophotometer is used for measuring the absorbance of a tetracycline solution at 357nm to determine the relative concentration of the tetracycline solution, so that the photocatalytic performance of the material is evaluated. The light source is a 300W xenon lamp (adopting a filter for filteringUltraviolet light, retention 400nm<λ<800nm visible light), the light source was 25cm from the reaction solution. At temperature and pH, 10mg of catalytic material was added followed by 0.9524g of sodium persulfate to a double-walled quartz reaction tube containing 100mL of a 20mg/L tetracycline solution. The xenon lamp was then turned on to perform the photocatalytic experiment under constant light and magnetic stirring. After the reaction, samples were taken every 5min, filtered through a 0.22 μm organic filter membrane, and then the absorbance of the filtrate at 357nm was measured using an ultraviolet-visible spectrophotometer, and converted to the relative mass concentration C (mg/L) of tetracycline according to a standard curve. According to C/C 0 Calculating the degradation rate (. eta.%) of tetracycline C 0 (mg/L) is the starting mass concentration of tetracycline.
η＝C/C 0 (1)
1, blank experiments (without catalyst) are respectively carried out under the condition of illumination; 2. adding only the catalyst iron oxyhydroxide; 3. adding catalysts of iron oxyhydroxide and persulfate Na 2 S 2 O 8 (ii) a 4. Adding catalysts of iron oxyhydroxide and persulfate Na under the condition of no light 2 S 2 O 8 . The degradation rate curve is shown in figure 2.
As can be seen from FIG. 2, at 40min, the degradation rate of tetracycline has reached 0.18 and there is a continuing trend to decrease.
Example 3
Preparation of the Standard Curve
Based on a tetracycline solution with an initial concentration of 100mg/L, solutions with concentrations of 5.00mg/L, 10.00mg/L, 20.00mg/L, 30.00mg/L, 40.00mg/L and 50.00mg/L are prepared, deionized water is used as a blank reference, the absorbance of each solution is measured at 357nm by an Shimadzu 2550 type ultraviolet-visible spectrophotometer, and a standard curve of the absorbance A-the concentration C of the tetracycline solution is obtained by linear fitting, as shown in FIG. 3.
The preparation method of the iron oxyhydroxide and the application of the iron oxyhydroxide in catalytic degradation of antibiotics by photo-synergetic activation persulfate have the advantages of easily obtained raw materials, lower cost, smaller forbidden bandwidth and smaller grain size of the prepared iron oxyhydroxide, mild antibiotic degradation reaction conditions, high degradation efficiency, capability of catalyzing the degradation of antibiotics under the sunlight condition, capability of obtaining good degradation efficiency without adding an extra electric field, remarkable degradation effect, easiness in recycling of the materials after catalytic degradation, capability of saving energy to the maximum extent while controlling environmental pollution, and no secondary pollution.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. The iron oxyhydroxide is characterized in that the iron oxyhydroxide is obtained by the following preparation method: (1) dispersing cetyl trimethyl ammonium bromide in deionized water, and stirring at room temperature for 30-60 min until the solution becomes transparent to obtain a solution A; (2) FeCl is added 3 Dissolving the mixture in the solution A, and stirring for 30-60 min at room temperature until a homogeneous solution is formed; (3) pouring the solution in the step (2) into a Teflon stainless steel high-pressure reaction kettle for hydrothermal reaction, and cooling to room temperature after the reaction is finished; (4) filtering under reduced pressure, washing the filter cake with ethanol and distilled water for 3 times respectively, and drying to obtain the iron oxyhydroxide.
2. The iron oxyhydroxide according to claim 1, wherein hexadecyl trimethyl ammonium bromide and FeCl are present in the step (1) and the step (2) 3 The molar ratio of FeCl to FeCl is 1: 1-1: 3, and FeCl is added in the step (2) 3 The concentration of (b) is 0.1 to 0.3 mol/L.
3. The iron oxyhydroxide according to claim 1, wherein the hydrothermal reaction temperature in the step (3) is 80 to 120 ℃ and the hydrothermal reaction time is 6 to 24 hours.
4. The iron oxyhydroxide according to claim 1, wherein the drying temperature in the step (4) is 50 to 60 ℃.
5. The application of the ferric hydroxide light synergistic activation persulfate to catalytically degrade the antibiotics is characterized by comprising the following steps of:
(1) placing the iron oxyhydroxide and the persulfate according to any one of claims 1 to 4 together in an aqueous antibiotic solution;
(2) and (3) placing the mixed solution in the step (1) under a xenon lamp for irradiating for 0.5-2 h, and stirring to degrade the antibiotics.
6. The use of the iron oxyhydroxide photo-synergistically activated persulfate as the catalytic degradation antibiotic according to claim 5, wherein the antibiotic is tetracycline.
7. The use according to claim 5, wherein the initial concentration of tetracycline is 10-100 mg/L.
8. The use according to claim 5, wherein the persulfate in the step (1) is sodium persulfate, potassium persulfate, sodium persulfate, potassium persulfate.
9. The use according to claim 5, wherein the ratio of ferric oxyhydroxide to the antibiotic solution in step (1) is 10-100 mg:100mL, and the ratio of persulfate to the antibiotic solution is 0.1-2 g:100 mL.
10. The use according to claim 5, wherein the visible light in the range of 400-800 nm is used in step (2).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210427751.6A CN114956194A (en) | 2022-04-22 | 2022-04-22 | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
| PCT/CN2022/118403 WO2023201974A1 (en) | 2022-04-22 | 2022-09-13 | Iron oxyhydroxide and use thereof in synergistic degradation of antibiotic with persulfate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210427751.6A CN114956194A (en) | 2022-04-22 | 2022-04-22 | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
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| CN114956194A true CN114956194A (en) | 2022-08-30 |
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| Country | Link |
|---|---|
| CN (1) | CN114956194A (en) |
| WO (1) | WO2023201974A1 (en) |
Cited By (1)
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| WO2023201974A1 (en) * | 2022-04-22 | 2023-10-26 | 浙江华源颜料股份有限公司 | Iron oxyhydroxide and use thereof in synergistic degradation of antibiotic with persulfate |
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