CN112661253A - Application of iron-based metal organic framework material in degradation of imidacloprid - Google Patents
Application of iron-based metal organic framework material in degradation of imidacloprid Download PDFInfo
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Abstract
The invention discloses an application of an iron-based metal organic framework material in degradation of imidacloprid, which comprises the following steps: under the condition that the iron-based metal organic framework material degrades imidacloprid, the iron agent metal organic framework material and the imidacloprid are contacted and react. The application method of the invention can effectively degrade imidacloprid, has good degradation effect, does not need expensive instruments or complicated pretreatment, and is economical, simple and efficient.
Description
Technical Field
The invention belongs to the technical field of imidacloprid degradation, and particularly relates to application of an iron-based metal-organic framework to imidacloprid degradation.
Background
Pesticides are chemical drugs used to prevent agricultural pests and to regulate plant growth. Wherein imidacloprid is a preferred neonicotinoid ultra-efficient insecticide and is widely used for protecting crops from pests. Due to high solubility and high stability, the water-soluble chitosan has more and more residues in water environment, seriously pollutes the ecological environment and threatens the human health.
At present, methods for treating pesticides mainly include physical methods (adsorption method), chemical precipitation methods (inorganic salts), biological removal methods, chemical photocatalytic degradation methods, advanced oxidation methods, and the like have been reported.
Wherein the adsorption method has the capability of efficiently removing the pesticide, has good application value, but is easy to generate secondary pollution. The chemical precipitation method is to precipitate the pesticide in the solution by adding a certain amount of inorganic salt, but needs to be circulated for many times to completely purify the pesticide. The biological removal process is highly selective and environmentally sensitive. The chemical photocatalytic degradation method mainly adopts the reaction of electron holes generated by a light-excited catalyst and water to generate OH free radicals to achieve the purpose of degrading pesticides, but most of light sources used in the research of the method are ultraviolet light, the ultraviolet light accounts for 4% of sunlight, and the utilization rate of the sunlight is low; the second majority of the photodegradation experiments are the photo-Fenton degradation, which still needs the help of H2O2Active species are generated and the photodegradation efficiency is low. Advanced oxidation processes have been extensively studied to decompose a variety of organic pollutants, mainly referred to as Fenton reactions and Fenton-like reactions, which are mainly confronted with the problems of Fe ion residues in aqueous solutions and the formation of H from the same2O2The OH radicals produced are unstable. Based on the above evaluation of various treatment methods, a method for removing imidacloprid with low cost, high activity, good stability and environmental friendliness needs to be found.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides the application of the iron-based metal organic framework material in the degradation of imidacloprid, firstly proposes the application of the iron-based metal organic framework material in the degradation of imidacloprid, adsorbs imidacloprid by utilizing the high porosity of metal organic framework Materials (MOFs), and then adds H2O2Combined with Fe in an iron-based metal organic framework2+/Fe3+The synergistic effect generates OH free radicals, thereby achieving the purpose of degrading imidacloprid by fenton-like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the application of the iron-based metal organic framework material in the degradation of imidacloprid comprises the following steps:
the iron-based metal organic framework material H2O2A fenton or fenton-like reaction occurs upon contact with imidacloprid under conditions that degrade imidacloprid.
In some embodiments, the application method comprises the steps of:
mixing the iron-based metal organic framework material and H2O2Adding the imidacloprid into the imidacloprid solution for reaction.
In some embodiments, the application method comprises the steps of:
firstly, adding the iron-based metal organic framework material into an imidacloprid solution to form a mixed solution for reaction, and then adding H2O2Further reaction occurs.
In some embodiments, the iron-based metal organic framework material is added into the imidacloprid solution to react for 30-60min, and then H is added2O2。
In some embodiments, the H is2O2Is 30 percent.
In some embodiments, the iron-based metal organic framework is Fe-MIL-88B-NH2And/or Fe-MIL-101-NH2。
In some embodiments, the concentration of the iron-based metal organic framework material in the mixed solution is 0.12-0.36 g/L.
In some embodiments, the 30% H2O2The addition amount of (B) is 0-40 mu L/50mL, H2O2The addition is > 0.
In some embodiments, the concentration of imidacloprid in the imidacloprid solution is 20-100 mg/L.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the imidacloprid is adsorbed according to the characteristics of high porosity and large specific surface area of the iron-based metal organic framework material, and then H is added2O2The Fenton-like reaction is generated to combine Fe in the iron-based metal organic framework2+/Fe3+The synergistic effect generates OH free radicals, the purpose of Fenton degradation of imidacloprid is achieved, the degradation effect is good (the degradation rate of the imidacloprid can reach more than 98.0 percent), and the imidacloprid in the imidacloprid solution can be almost completely degraded.
In addition, the method for removing imidacloprid does not need expensive instruments and complex pretreatment, and is economical, simple and efficient.
Drawings
FIG. 1 is a reaction schematic diagram of the preparation of the metal-organic framework based on iron and the degradation of imidacloprid in the embodiment of the present invention;
FIG. 2 shows Fe-MIL-88B-NH in the present invention2And Fe-MIL-101-NH2A comparative graph of the degradation effect of imidacloprid and the traditional Fenton degradation effect;
FIG. 3 shows different concentrations of Fe-MIL-88B-NH2Degradation effect on imidacloprid;
FIG. 4 shows different concentrations of Fe-MIL-101-NH2Degradation effect on imidacloprid;
FIG. 5 shows Fe-MIL-88B-NH2Degradation effect in imidacloprid aqueous solution with different concentrations;
FIG. 6 shows Fe-MIL-101-NH2Degradation effect in imidacloprid aqueous solution with different concentrations;
FIG. 7 shows the addition of Fe-MIL-88B-NH2After the reaction, H2O2The degradation effect of the imidacloprid is different;
FIG. 8 is the first addition of Fe-MIL-101-NH2After the reaction, H2O2The different dosage of the imidacloprid has the degradation effect on imidacloprid.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As shown in fig. 1, to achieve the above object of the present invention, the specific embodiment of the present invention provides a process flow of preparing an iron-based metal organic framework material, preparing an imidacloprid standard working curve, performing an adsorption power experiment and an isothermal adsorption experiment, allowing the iron-based metal organic framework material to contact and react with imidacloprid under different conditions, and detecting a reaction result product HPLC-MS, which specifically comprises the following steps:
(1) preparation of iron-based metal organic framework material (Fe-based MOF): the iron-based metal organic framework material used in the following examples is specifically Fe-MIL-88B-NH2And Fe-MIL-101-NH2The preparation method comprises the following steps:
①Fe-MIL-88B-NH2the preparation of (1): synthesized by a hot solvent method, and FeCl with equal molar ratio is firstly synthesized3·6H2O and 2-amino terephthalic acid (NH)2-BDC) was dissolved in 42mL of N, N-Dimethylformamide (DMF) and stirred vigorously at room temperature for 1 h; subsequently, the mixture was transferred to a 100mL reaction vessel and heat-treated at 110 ℃ for 12 hours; after cooling to room temperature, it was centrifuged at 8000rpm for 5min, washed three times with DMF and ethanol (EtOH) and finally the product was dried in a vacuum oven at 70 ℃ overnight.
②Fe-MIL-101-NH2The preparation of (1): synthesized by a hot solvent method, FeCl with a molar ratio of 2:1 is firstly added3·6H2O and NH2BDC dissolved in 40mL DMF and stirred vigorously at room temperature for 1 h; subsequently, the mixture was transferred to a 100mL reaction vessel and heat-treated at 110 ℃ for 20 hours; after treatment like Fe-MIL-88B-NH2And (4) preparing.
(2) Drawing an imidacloprid standard working curve:
preparing 100mg/L imidacloprid mother liquor, diluting the imidacloprid mother liquor into 1, 2, 5, 10, 20, 50 and 100mg/L solutions according to gradient, and then respectively filling the solutions into liquid phase sample injection vials; quantitative analysis for the detection of imidacloprid using a liquid chromatography (HPLC) system with a C18 column (4.6X 250mm particle size 5 μm) using a mobile phase consisting of water/acetonitrile (70: 30, v/v); detection was performed at 270nm with a Diode Array Detector (DAD) at a column temperature of 30 ℃ at a rate of 1 mL/min.
(3) Adsorption power experiment and isothermal adsorption experiment:
adsorption power experiment: preparing 100mL of imidacloprid standard solution 60mg/L, taking a proper amount of iron-based metal organic framework material in the imidacloprid solution, uniformly stirring by using a magnetic stirrer, and sampling at 0, 5, 10, 20, 30, 40, 50, 60, 120, 180 and 240min respectively. 0.5mL of the sample solution was aspirated by a disposable syringe, and the sample solution was filtered through a 0.22 μm water membrane and subjected to post-liquid phase measurement.
② isothermal adsorption experiment: 100mL of imidacloprid standard solutions (10, 30, 50, 70 and 90mg/L) with different concentrations are prepared, and sampling is carried out after 60min respectively, and liquid phase measurement is carried out after filtration by using a 0.22 mu m water film.
(4) The experimental conditions are as follows: and (3) investigating the influence of the concentration of the iron-based metal organic framework material, the concentration of the imidacloprid solution and the dosage of hydrogen peroxide on the removal of the imidacloprid.
(5) HPLC-MS detection of degradation products: mobile phase: water/acetonitrile (50:50, v/v); flow rate: 0.4 mL/min; imidacloprid parent ion: 256.1, daughter ion: 209.0/175.1.
Examples 1 to 4
With Fe-MIL-88B-NH2Taking different Fe-MIL-88B-NH as variable dosage2The amount of the compound is added into 20mL imidacloprid solution with the concentration of 60mg/L (pH is 6.4) to form mixed solution, and Fe-MIL-88B-NH in the mixed solution2The concentrations are different; after the mixed solution was adsorbed for 60min under magnetic stirring, 1mL of the solution was aspirated, and the sample was collected by 0.22 μm water membrane filtration using a sample injection vial, followed by adding 40 μ L/50mL of 30% by mass H to the reaction system2O2And carrying out Fenton-like degradation for 90min, and collecting a sample by the same method to carry out liquid phase detection.
The formula for the removal rate is as follows:
different dosages of Fe-MIL-88B-NH2The degradation effect on imidacloprid is shown in figure 3.
Examples 5 to 8
With Fe-MIL-101-NH2Taking different Fe-MIL-101-NH as variable dosage2The amount of the imidacloprid is added into 20mL of imidacloprid solution with the concentration of 60mg/L (pH is 6.4) to form mixed solution, and Fe-MIL-101-NH is added into the mixed solution2Are different in concentration; after the mixed solution was adsorbed for 60min under magnetic stirring, 1mL of the solution was aspirated, and the sample was collected by 0.22 μm water membrane filtration using a sample injection vial, followed by adding 40 μ L/50mL of 30% by mass H to the reaction system2O2And carrying out Fenton-like degradation for 90min, and collecting a sample by the same method to carry out liquid phase detection. The formula for the removal rate is shown in example 1.
Different dosages of Fe-MIL-101-NH2The degradation effect on imidacloprid is shown in figure 4.
Examples 9 to 12
The imidacloprid solution with different concentrations is taken as a variable, and the rest experimental conditions are as follows: Fe-MIL-88B-NH2The concentration is 0.3g/L, the pH is 6.4, after the mixed solution is adsorbed for 60min under magnetic stirring, 1mL of the solution is absorbed, a sample is collected by a sample injection vial for 0.22 μm water membrane filtration, and then 40 μ L/50mL of H with the mass fraction of 30% is added into the reaction system2O2And carrying out Fenton-like degradation for 90min, and collecting a sample by the same method to carry out liquid phase detection.
The results of the detection are shown in FIG. 5.
Examples 13 to 16
The imidacloprid solution with different concentrations is taken as a variable, and the rest experimental conditions are as follows: Fe-MIL-101-NH2The concentration was 0.24g/L, pH was 6.4, and after the mixed solution was adsorbed under magnetic stirring for 60min, 1mL of the solution was aspirated, and the sample was collected by 0.22 μm water membrane filtration using a sample injection vial, followed by adding 40 μ L H to the reaction system2O2And carrying out Fenton-like degradation for 90min, and collecting a sample by the same method to carry out liquid phase detection.
The results of the detection are shown in FIG. 6.
Examples 17 to 20
With a different H2O2The addition amount of (a) is a variable, and the rest experimental conditions are as follows: the concentration of the imidacloprid solution is 60mg/L, Fe-MIL-88B-NH2The dosage is 0.3g/L, pH is 6.4, the mixed solution is adsorbed for 60min under magnetic stirring, 1mL of the solution is absorbed, a sample is collected by a sample injection vial for 0.22 μm water membrane filtration, and then 30% H by mass fraction is respectively added into the reaction system2O2The amount of the compound is 0, 10 mu L/50mL, 20 mu L/50mL, 30 mu L/50mL, 40 mu L/50mL, Fenton-like degradation is carried out for 90min, and samples are collected by the same method and subjected to liquid phase detection.
The results of the detection are shown in FIG. 7.
Examples 21 to 24
With a different H2O2The addition amount of (a) is a variable, and the rest experimental conditions are as follows: the concentration of the imidacloprid solution is 60mg/L, Fe-MIL-101-NH2The dosage is 0.24g/L, the pH is 6.4, after the mixed solution is adsorbed for 60min under magnetic stirring, 1mL of the solution is absorbed, a sample is collected by a sample injection vial for 0.22 mu m water film filtration, and then 30 percent by mass of H is respectively added into the reaction system2O2The amount of the compound is 0, 10 mu L/50mL, 20 mu L/50mL, 30 mu L/50mL, 40 mu L/50mL, Fenton-like degradation is carried out for 90min, and samples are collected by the same method and subjected to liquid phase detection.
The detection results are shown in fig. 8.
Based on the experimental results of the above examples, the best mode of the present invention is as follows:
when Fe-MIL-88B-NH is used2And H2O2When the combination generates Fenton or Fenton-like reaction to degrade the imidacloprid, the concentration of the imidacloprid in the imidacloprid solution is 20mg/L, and Fe-MIL-88B-NH2The dosage of the (B) is 0.3-0.36g/L, the pH of the solution is 6.4, after the solution is adsorbed for 60min under magnetic stirring, 40 mu L/50mL of H with the mass fraction of 30 percent is added into a reaction system2O2And then reacting for 90 min;
when using Fe-MIL-101-NH2And H2O2When the combination generates Fenton or Fenton-like reaction to degrade the imidacloprid, the concentration of the imidacloprid in the imidacloprid solution is 20-60mg/L, and Fe-MIL-101-NH2The dosage of the (B) is 24-36g/L, the pH of the solution is 6.4, after 30-60min under magnetic stirring, 40 is added into the reaction systemmu.L/50 mL of H with the mass fraction of 30%2O2And then reacting for 30-90 min.
Through detection, the degradation rate of the optimal implementation scheme on imidacloprid can reach more than 98%.
Examples 25 to 26
Taking two parts of imidacloprid solution, wherein one part is imidacloprid with the concentration of 20mg/L, pH of 6.4, and adding 0.3mg/L Fe-MIL-88B-NH2After 60min of adsorption under magnetic stirring, 40. mu.L of H is added into the reaction system2O2Carrying out Fenton-like degradation for 90 min; the other part of Fe-MIL-101-NH with the imidacloprid concentration of 60mg/L, pH of 6.4 and 0.24mg/L2After 60min of adsorption under magnetic stirring, 40 mul/50 mL of H with the mass fraction of 30% is added into the reaction system2O2Carrying out Fenton-like degradation for 90 min;
the sample is collected by the same method and is subjected to liquid phase detection, and the detection result is shown in FIG. 2.
Comparative example 1
Comparative example 1 is a blank control experiment, the experiment was carried out without adding a degradation agent during the experiment, and then the samples were collected by the same method to carry out liquid phase detection, and the detection results are shown in fig. 2.
Comparative example 2
Comparative example 2 differs from example 25 in that only 40. mu.L/50 mL of 30% by mass H was added to the imidacloprid solution2O2After the reaction is completed, a sample is collected by the same method and subjected to liquid phase detection, and the detection result is shown in fig. 2.
Comparative example 3
Comparative example 3 differs from example 25 in that 0.3g/L ferrous iron solution (Fe) was added to the imidacloprid solution2+) After the reaction is completed, a sample is collected by the same method and subjected to liquid phase detection, and the detection result is shown in fig. 2.
Comparative example 4
Comparative example 3 differs from example 25 in that 0.3g/L ferrous iron solution (Fe) was added to the imidacloprid solution2+) After reacting for 60min, 40. mu.L of H was added to the reaction system2O2After the reaction is finished, collecting a sample by the same method to carry out liquid phase detection, wherein the detection result is shown in figure 2Shown in the figure.
As can be seen from FIG. 2, the degradation rate of imidacloprid by using the method of the invention is extremely high, and can reach more than 98.0%; and the degradation rate of the imidacloprid is less than 60 percent by using the traditional method (such as comparative example 4).
In conclusion, the imidacloprid degradation by using the iron-based metal organic framework material has excellent degradation effect, mild conditions, simple and economic reaction conditions and high reaction efficiency, can react in a solution close to neutral (pH6.4), and can complete the imidacloprid degradation in a short time.
In addition, the iron-based metal organic framework material has high reuse rate, can be recycled, and has better imidacloprid removal effect than the removal effect of the existing method after being recycled for 5 times.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The application of the iron-based metal organic framework material in the degradation of imidacloprid is characterized in that the application method comprises the following steps:
mixing the iron-based metal organic framework material and H2O2A fenton or fenton-like reaction occurs upon contact with imidacloprid under conditions that degrade imidacloprid.
2. The application according to claim 1, characterized in that the application method comprises the following steps:
mixing the iron-based metal organic framework material and H2O2Adding the imidacloprid into the imidacloprid solution for reaction.
3. The application according to claim 1, characterized in that the application method comprises the following steps:
firstly, adding the iron-based metal organic framework material into an imidacloprid solution to form a mixed solution for reaction, and then adding H2O2Further reaction occurs.
4. The application of claim 3, wherein the iron-based metal organic framework material is added into an imidacloprid solution to react for 30-60min, and then H is added2O2。
5. Use according to claim 4, wherein H is2O2Is 30 percent.
6. Use according to any one of claims 1 to 5, wherein the iron-based metal organic framework material is Fe-MIL-88B-NH2And/or Fe-MIL-101-NH2。
7. The use according to any one of claims 1 to 5, wherein the concentration of the iron-based metal organic framework material in the mixed solution is 0.12 to 0.36 g/L.
8. Use according to any one of claims 1 to 5, wherein said 30% H2O2The amount of (B) added is 0 to 40. mu.L/50 mL.
9. The use according to any one of claims 1 to 5, wherein the imidacloprid solution has an imidacloprid concentration of 20-100 mg/L.
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| CN113527700A (en) * | 2021-06-28 | 2021-10-22 | 长沙理工大学 | Method for regulating and controlling catalytic activity of MIL-88 material |
| CN114177944A (en) * | 2021-11-24 | 2022-03-15 | 北京农学院 | Visible light catalytic degradation anabasine pesticide of metal organic framework compound |
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| CN106475144A (en) * | 2016-09-28 | 2017-03-08 | 济南大学 | A kind of type Fenton catalyst preparation method based on ferrous metals organic framework material |
| CN108393097A (en) * | 2018-05-15 | 2018-08-14 | 济南大学 | A kind of ferrous metals containing redox mediators-organic framework material type Fenton catalyst preparation method |
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| CN106475144A (en) * | 2016-09-28 | 2017-03-08 | 济南大学 | A kind of type Fenton catalyst preparation method based on ferrous metals organic framework material |
| CN108393097A (en) * | 2018-05-15 | 2018-08-14 | 济南大学 | A kind of ferrous metals containing redox mediators-organic framework material type Fenton catalyst preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113527700A (en) * | 2021-06-28 | 2021-10-22 | 长沙理工大学 | Method for regulating and controlling catalytic activity of MIL-88 material |
| CN114177944A (en) * | 2021-11-24 | 2022-03-15 | 北京农学院 | Visible light catalytic degradation anabasine pesticide of metal organic framework compound |
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