CN116060078B - photo-Fenton catalyst and preparation method and application thereof - Google Patents
photo-Fenton catalyst and preparation method and application thereof Download PDFInfo
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Images
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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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- 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
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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
- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- 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
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- 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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Abstract
The invention relates to a photo-Fenton catalyst and a preparation method and application thereof. The light passes through Cu from Fenton catalyst 0 @CuO x NC and Zn 2 In 2 S 5 The composite material is obtained according to a certain mass ratio, can be applied to photo-Fenton degradation of antibiotic wastewater, and has excellent degradation effect on tetracycline. The invention prepares Cu by utilizing a hydrothermal method and a chemical precipitation method 0 @CuO x ‑NC/Zn 2 In 2 S 5 The composite material has the remarkable characteristics of simple preparation method, and has important application value and market prospect.
Description
Technical Field
The invention relates to the technical field of semiconductor photo Fenton, in particular to a photo Fenton catalyst and a preparation method and application thereof.
Background
Advanced Oxidation Process (AOP) is used as research hot spot for degrading high biotoxicity and biological refractory organic matters in sewage in recent years, and can generate high-activity hydroxyl free radical (OH) or other free radicals in the oxidation process, so that refractory organic pollutants are oxidized and decomposed into other small molecular compounds in a non-selective way, and even are directly oxidized into CO 2 And H 2 O. Wherein the Fenton method is used as an advanced oxidation method, and the principle is that Fe is utilized 2+ Catalytic H 2 O 2 OH is generated, and organic matters which are difficult to degrade in the sewage are removed by oxidation.
Hospitals, aquaculture, livestock farming and pharmaceutical plants are the main sources of use and emission of antibiotic pollutants. Tetracyclines (Tetracyclines) are produced by actinomycetes or are prepared by semisynthesis, such as aureomycin, oxytetracycline (OTC), TC, semisynthetic derivatives minocycline, doxycycline, metacycline and the like, and share the common feature that the structures all use hydrogenated tetracenes as parent nuclei, have common phenanthrane, and the antibacterial effect is obviously reduced if the ring substituents are changed. The Fenton oxidation process can be used for large scale treatment of antibiotics, but has two distinct disadvantages: (1) The reaction needs an acidic (pH is approximately equal to 3.0) environment, the waste water needs to be acidified before the reaction, and the acidified water body needs to be reprocessed after the reaction; and (2) the recycling process of the iron mud is difficult. The advent of photocatalytic in situ self-Fenton perfectly addresses the shortcomings of Fenton systems, and research on photo-self-Fenton catalysts is continually being explored.
Disclosure of Invention
The invention aims to provide a photo-self Fenton catalyst and a preparation method and application thereof, so as to solve the problems in the prior art and realize an excellent photo-catalytic in-situ self Fenton degradation effect on antibiotics.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a preparation method of a photo-Fenton catalyst, which comprises the following steps:
Cu 0 @CuO x -NC preparation: reacting Cu salt, beta-cyclodextrin and urea in a solvent, drying the obtained reactant, performing two-step annealing treatment under protective atmosphere, washing and drying to obtain the Cu 0 @CuO x -NC; wherein x < 1;
the protective atmosphere is nitrogen; the solvent is preferably ethanol.
Zn 2 In 2 S 5 Is prepared from the following steps:
taking Zn salt, in salt and thioacetamide as raw materials to carry out hydrothermal reaction to obtain Zn 2 In 2 S 5 ;
Preparation of the photo-self Fenton catalyst:
cu is added with 0 @CuO x NC and Zn 2 In 2 S 5 According to different mass ratios (Cu 0 @CuO x NC and Zn 2 In 2 S 5 The mass ratio of the copper alloy to the copper alloy is 1wt% -10 wt%) is compounded in a solvent to obtain Cu 0 @CuO x -NC/Zn 2 In 2 S 5 And the composite material is the photo-Fenton catalyst.
Further, the molar ratio of the Cu salt, the beta-cyclodextrin and the urea is 2:1:75.
Further, cu 0 @CuO x In the preparation of NC, the reaction temperature in the solvent is 60-100 ℃ and the reaction time is 3h-8h.
Further, the two-step annealing treatment is as follows:after being kept at 400-500 ℃ for 1-2 h, the mixture is kept at 700-800 ℃ for 1-2 h. Further, the temperature rising rate in the two-step annealing treatment process is 1-5 ℃ min -1 。
Further, the molar ratio of Zn salt, in salt and thioacetamide is 2:2:10.
Further, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 10-24 hours.
The invention also provides the photo-self Fenton catalyst prepared by the preparation method.
The invention further provides application of the photo-Fenton catalyst in degrading antibiotics; in particular to a water body containing antibiotics.
Further, the antibiotic is tetracycline.
In addition to the iron-based phase, other transition, rare earth and noble metal phases also have activated H 2 O 2 The ability to form OH, the reaction mechanism of which is equal to that of Fe 2+ With similarity, M represents different transition/rare earth/noble metal elements, M n+ Producing OH and being oxidized to M (n +1)+ Oxidized M (n+1)+ And can also be H 2 O 2 Reduction to M n+ Promoting H while achieving catalyst regeneration 2 O 2 And improves the reaction rate of the system.
Cu to be prepared by the invention 0 @CuO x -NC replaces iron-based, utilizing H generated in the system 2 O 2 Realize in situ self-Fenton degradation of TC.
The invention discloses the following technical effects:
the invention prepares the Cu 0 @CuO x NC vs Zn 2 In 2 S 5 The catalyst prepared by the improvement can be applied to Yu Guangzi Fenton degradation of antibiotic wastewater and phenolic wastewater, and particularly has excellent degradation effect on tetracycline.
The invention prepares Cu by utilizing a hydrothermal method and a chemical precipitation method 0 @CuO x -NC/Zn 2 In 2 S 5 The composite material has the remarkable characteristics of simple preparation method, important application value and marketScene prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows H production in pure water by the product of each step of example 1 of the present invention 2 O 2 (a) And decomposing 1 mmol.L -1 H of (2) 2 O 2 Curve (b);
FIG. 2 shows the TC curve (a), the corresponding K value (b) and H production during degradation for the product of example 1 of the present invention 2 O 2 Curve (c);
FIG. 3 is an XRD pattern of the product of each step of example 1 of the present invention; a is ZnIS and Cu 0 @CuO x XRD patterns of NC, b is the XRD patterns of CuZS-1, cuZS-5 and CuZS-10.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
Cu for in situ self-Fenton degradation of TC 0 @CuO x -NC/Zn 2 In 2 S 5 Preparation of the catalyst:
(1)Cu 0 @CuO x preparation of the NC
0.6307g of CuCl 2 ·2H 2 O, 2g of beta-cyclodextrin, 8g of urea are dissolved in 60mL of ethanol, stirred in a water bath at 80℃until the solvent has evaporated completely, and subsequently dried in an oven at 60 ℃.
Grinding the obtained material, placing into quartz boat, introducing N into tube furnace 2 Two annealing reactions were carried out (first at 5 ℃ C. Min -1 Is maintained at 500 ℃ for 2h and then at 5 ℃ for min -1 Is maintained at a temperature rise rate of 2h at 800 c). The resulting material was alternately washed with deionized water and ethanol and dried in a vacuum oven at 60 c, designated Cu 0 @CuOx-NC。
(2)Zn 2 In 2 S 5 (ZIS) preparation
2 mmol of ZnSO 4 ⋅7H 2 O and 2 mmol of InCl 3 ⋅6H 2 O is dissolved in 30 mL for dissociationAfter the solution was clarified by stirring in a mixed solution of child water and 20 mL glycerol, 10 mmol of thioacetamide was added thereto, and the mixture was transferred to a high-pressure reaction vessel of 100 mL polytetrafluoroethylene after stirring for 1 hour, and subjected to hydrothermal reaction at 160℃for 12 h. After cooling to room temperature, the yellow precipitate was washed 3 times with deionized water and ethanol, respectively, and dried in a vacuum oven at 60 ℃.
(3)Cu 0 @CuO x -NC/Zn 2 In 2 S 5 Preparation of composite materials
Cu with different mass ratios 0 @CuO x NC and Zn 2 In 2 S 5 Dispersing into 20 mL ethanol, stirring thoroughly in water bath at 70deg.C until ethanol is completely evaporated, washing the obtained powder with deionized water, and drying in vacuum oven (temperature 60 deg.C).
The samples compounded in different mass ratios were designated CuZS-X, examples 2-3 were designated CuZS-1 (Cu 0 @CuO x NC and Zn 2 In 2 S 5 Is 1 to wt percent by mass and CuZS-5 (Cu) 0 @CuO x NC and Zn 2 In 2 S 5 Is 5. 5 wt%) and CuZS-10 (Cu) 0 @CuO x NC and Zn 2 In 2 S 5 The effect was explained by taking 10wt% of the mass ratio as an example.
Example 2
Cu 0 @CuO x -NC/Zn 2 In 2 S 5 Production of H by composite material in pure water 2 O 2 And decomposing 1 mmol.L -1 H 2 O 2 Is verified by the following steps:
and (3) taking a 3W LED lamp as a light source, and carrying out dark adsorption on the products in each step in the embodiment 1 for 40min and simultaneously introducing oxygen to reach saturation of dissolved oxygen before illumination. After the light source is turned on, sampling every 10 min, the volume of the sampled sample is about 2 mL, adding 1 mL color developing agent, and testing H at 400 nm by titanium salt spectrophotometry after developing for 10 min 2 O 2 Is a concentration of (3). No sacrificial agent was added during the test.
FIG. 1 shows H production in pure water by the product of each step of example 1 of the present invention 2 O 2 (a) And decomposition of1 mmol·L -1 H of (2) 2 O 2 Curve (b).
H in pure water 2 O 2 The concentration is changed with time as shown in FIG. 1a, pure Cu 0 @CuO x NC and Zn 2 In 2 S 5 H generated after 60 min of visible light irradiation 2 O 2 The concentrations are 19 mu mol L respectively -1 And 26. Mu. Mol L -1 . Photocatalytic H production of CuZS-1, cuZS-5 and CuZS-10 composite material 2 O 2 The effect is greatly improved, wherein the H of CuZS-5 2 O 2 The best yield is 0.13 mmol L -1 。
H of the catalyst 2 O 2 The decomposition effect is critical to Fenton and Fenton-like reactions because the catalyst decomposes H 2 O 2 Reactive Oxygen Species (ROS) are generated, and especially OH has strong oxidizing ability to wastewater.
As can be seen from fig. 1b, due to H 2 O 2 With Cu 0 @CuO x Complexing of Cu element on NC surface, pure Cu under irradiation of visible light 0 @CuO x NC can decompose H very quickly 2 O 2 . For CuZS-X composites, in Zn 2 In 2 S 5 Adding Cu0@CuO x -NC rear H 2 O 2 Significantly enhanced decomposition behavior, in particular H of CuZS-5 2 O 2 The decomposition rate can reach 41.2 percent, which is beneficial to the in-situ generation of H 2 O 2 The next degradation experiment was performed.
Example 3
The LED lamp of 3W is adopted to simulate visible light, and the initial concentration of TC simulated wastewater is 30 mg.L -1 The solution volume was 50 mL and the catalyst loading was 25 mg. Before the photocatalytic reaction, the TC suspension containing the catalyst is dispersed in an ultrasonic way, and then stirred and adsorbed for 40min under dark condition to reach adsorption and desorption equilibrium. After the light source was turned on, samples were taken every 10 minutes, and the volume of the sample was about 3 mL. After filtering the sample solution, the TC concentration was measured by UV-visible spectrophotometer and passed through C/C 0 Judging the degradation effect. Wherein C is 0 For the concentration of TC after adsorption equilibrium,c is the concentration of TC at reaction time t.
FIG. 2 shows the TC curve (a), the corresponding K value (b) and H production during degradation for the products of example 1 2 O 2 Curve (c).
As shown in FIG. 2a, the performance of the CuZS-1, cuZS-5 and CuZS-10 composites is significantly higher than that of pure Cu 0 @CuO x NC and Zn 2 In 2 S 5 The removal rate of the CuZS-5 to TC can reach 89.3% in 60 min.
As can be seen from FIG. 2b, the k value of CuZS-5 is 0.032 min -1 Is pure Zn 2 In 2 S 5 Is 2.1 times (0.015 min) -1 ) And pure Cu 0 @CuO x 8.0 times NC (0.004 min -1 ). Under such conditions, TC acts as a hole-sacrificing agent to simultaneously accelerate H in solution 2 O 2 Is generated in Zn 2 In 2 S 5 And H in CuZS-5 2 O 2 The production amount of H is higher than that of pure water without a sacrificial agent 2 O 2 Yield, but H of CuZS-5 in TC solution 2 O 2 The content is 0.65 mmol.L -1 Slightly lower than that of pure Zn 2 In 2 S 5 Yield of (0.78 mmol.L) -1 ) Probably because most of H is generated in situ in the CuZS-5 system 2 O 2 Is used to generate ROS to promote TC degradation.
Figure 3 is an XRD pattern of the product of each step in example 1. As can be seen from FIG. 3, pure Cu 0 @CuO x The characteristic peak of NC at 2θ=24.4° is broad, corresponding to amorphous nitrogen-doped graphitic carbon (NC), the other three characteristic peaks being Cu at 43.5 °, 50.4 ° and 74.2 °, respectively 0 The (111), (200) and (220) planes of (PDF card 99-0034), in addition, there is a weak characteristic peak at 36.3 DEG, corresponding to Cu 2 O (PDF card 05-0667).
Pure Zn 2 In 2 S 5 Is hexagonal Zn reported in literature 2 In 2 S 5 Is completely consistent.
XRD diffraction patterns of CuZS-1, cuZS-5 and CuZS-10 show the same effect as Zn 2 In 2 S 5 Similar profile, and the peak intensities of CuZS-1, cuZS-5 and CuZS-10 are obviously weaker than that of pure Zn 2 In 2 S 5 Description of Cu 0 @CuO x NC and Zn 2 In 2 S 5 There is an interaction between them.
The invention utilizes a small amount of Cu 0 @CuO x NC vs Zn 2 In 2 S 5 The light self Fenton degradation efficiency can be obviously improved by modification, and the popularization and application value is good.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (7)
1. An application of a photo-Fenton catalyst in the degradation of tetracycline, which is characterized in that the preparation method of the photo-Fenton catalyst comprises the following steps:
Cu 0 @CuO x -NC preparation: reacting Cu salt, beta-cyclodextrin and urea in a solvent, drying the obtained reactant, performing two-step annealing treatment under protective atmosphere, washing and drying to obtain the Cu 0 @CuO x -NC;
Zn 2 In 2 S 5 Is prepared from the following steps:
taking Zn salt, in salt and thioacetamide as raw materials to carry out hydrothermal reaction to obtain Zn 2 In 2 S 5 ;
Preparation of the photo-self Fenton catalyst:
cu is added with 0 @CuO x NC and Zn 2 In 2 S 5 Compounding in solvent to obtain Cu 0 @CuO x -NC/Zn 2 In 2 S 5 And the composite material is the photo-Fenton catalyst.
2. Use according to claim 1, characterized in that the molar ratio of Cu-salt, β -cyclodextrin and urea is 2:1:75.
3. The use according to claim 1, characterized in that Cu 0 @CuO x In the preparation of NC, the reaction temperature in the solvent is 60-100 ℃ and the reaction time is 3-8 h.
4. The use according to claim 1, wherein the two-step annealing process is: after being kept at 400-500 ℃ for 1-2 h, the mixture is kept at 700-800 ℃ for 1-2 h.
5. The method according to claim 4, wherein the temperature rise rate during the two-step annealing treatment is 1-5 ℃ min -1 。
6. Use according to claim 1, characterized In that the molar ratio of Zn salt, in salt and thioacetamide is 2:2:10.
7. The use according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120-180 ℃ for a time of 10-24 hours.
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