CN114471617B - Magnetic photocatalyst, preparation method and application thereof - Google Patents

Magnetic photocatalyst, preparation method and application thereof Download PDF

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CN114471617B
CN114471617B CN202210287110.5A CN202210287110A CN114471617B CN 114471617 B CN114471617 B CN 114471617B CN 202210287110 A CN202210287110 A CN 202210287110A CN 114471617 B CN114471617 B CN 114471617B
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CN114471617A (en
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李本侠
卢先春
郑自强
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Zhejiang Sci Tech University ZSTU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33Electric or magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a magnetic photocatalyst, a preparation method and application thereof; the preparation method comprises the following preparation steps: fe is added to 3 O 4 Dispersing the powder in water, adding organic molecules with polyfunctional groups and easy to carbonize, cadmium-containing compounds and sulfur-containing compounds, reacting at a certain temperature to obtain a precipitate, washing and drying the precipitate to obtain Fe 3 O 4 @cds@cqds powder; the magnetic photocatalyst is provided to solve the technical problems that in the prior art, the synthesis of the semiconductor surface modified carbon quantum dots commonly has multi-step phenomenon, namely, the carbon quantum dots are synthesized firstly and then are compounded with the semiconductor material, and the multi-step synthesis can cause uneven distribution of the carbon quantum dots on the semiconductor surface, unstable combination and complicated process.

Description

Magnetic photocatalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of heterogeneous catalytic material preparation, in particular to a magnetic photocatalyst, a preparation method and application thereof.
Background
Sewage discharge has become one of the main sources of groundwater and river pollution in China, which not only affects ecological environment construction, but also brings health risks to people. For example, residues of antibiotics in sewage in aquatic environments can induce the development of drug-resistant pathogens, creating a potential long-term hazard to human health. The currently used sewage treatment technologies include: fenton oxidation, ozone oxidation, photocatalytic oxidation, supercritical water oxidation, electrochemical oxidation and other technologies. The photocatalytic oxidation technology has the advantages of rapid reaction, mild condition, strong oxidizing capability, low cost, no pollution, recycling and the like, and has proved to be a green sustainable strategy for sewage treatment. However, the existing single-purity semiconductor material has the defects of high photon-generated carrier recombination rate, insufficient surface active sites and the like, so that the single-purity semiconductor material has lower photocatalytic activity. In addition, the catalyst powder is difficult to separate, recycle and use after the sewage treatment is completed, so that the practical application of the photocatalytic oxidation technology in the aspect of sewage treatment is limited.
It is known that wrapping the semiconductor on the magnetic surface not only can improve the circulation stability of the catalyst, but also can facilitate the recycling of the treated sewage. In addition, the modification of Carbon Quantum Dots (CQDs) on the surface of the semiconductor material can promote the separation of photon-generated carriers, and is beneficial to the adsorption of target pollutants in sewage, so that the photocatalytic performance is improved. In the prior report, the synthesis of the semiconductor surface modified carbon quantum dot generally has a multi-step phenomenon, namely, the carbon quantum dot is synthesized firstly and then is compounded with a semiconductor material, the multi-step synthesis possibly causes uneven distribution and unstable combination of the carbon quantum dot on the surface of the semiconductor, and the process is complicated.
Accordingly, the present invention has been made in view of the above problems, and it is desirable to provide a magnetic photocatalyst, a method for preparing the same, and applications thereof.
Disclosure of Invention
The invention aims to provide a magnetic photocatalyst, a preparation method and application thereof, and aims to solve the technical problems that in the prior art, the synthesis of semiconductor surface modified carbon quantum dots commonly has multi-step phenomenon, namely, the carbon quantum dots are synthesized firstly and then are compounded with a semiconductor material, and the multi-step synthesis can cause uneven distribution, unstable combination and complicated process of the carbon quantum dots on the semiconductor surface.
The invention provides a preparation method of a magnetic photocatalyst, which comprises the following preparation steps:
fe is added to 3 O 4 Dispersing the powder in water, addingAdding organic molecules containing polyfunctional groups and easy to carbonize, cadmium-containing compounds and sulfur-containing compounds, reacting at a certain temperature to obtain a precipitate, washing and drying the precipitate to obtain Fe 3 O 4 @cds@cqds powder.
Preferably, fe 3 O 4 Dispersing the powder in water, adding organic molecule with multiple easily carbonizable functional groups, cadmium-containing compound and sulfur-containing compound, mixing, reacting at 160-200deg.C for 3-7 hr, cooling to room temperature to obtain precipitate, washing and drying to obtain Fe 3 O 4 @cds@cqds powder.
Preferably, the multifunctional group-containing carbonizable organic molecule is ascorbic acid or glucose.
Preferably, the multifunctional group-containing easily carbonizable organic molecule is ascorbic acid; ascorbic acid, cadmium element, fe 3 O 4 The molar ratio of the sulfur elements is as follows: (2-21): (16-24): (20-30): (25-37).
Preferably Fe 3 O 4 When the powder is dispersed in water, fe 3 O 4 The mass ratio of the water to the water is (1-3) 1000.
Preferably Fe 3 O 4 The preparation method of the powder comprises the following steps: dissolving ferric trichloride hexahydrate, trisodium citrate dihydrate and anhydrous sodium acetate in ethylene glycol, mixing, reacting at 180-220 ℃ for 8-12h, cooling to room temperature, collecting precipitate, and drying to obtain Fe 3 O 4 And (3) powder.
Preferably, the mass ratio of ferric trichloride hexahydrate, trisodium citrate dihydrate, anhydrous sodium acetate and ethylene glycol is (9-13): (3-6): (17-25): (310-470).
Preferably Fe 3 O 4 The particle size of the powder is less than or equal to 300nm.
The invention also provides a magnetic photocatalyst obtained based on the preparation method of the magnetic photocatalyst, which comprises Fe 3 O 4 Powder, fe 3 O 4 The powder is wrapped with CdS, and the carbon quantum dots are uniformly distributed on the surface of the CdS.
The invention also provides an application of the magnetic photocatalyst in sewage treatment.
Compared with the prior art, the magnetic photocatalyst provided by the invention has the following advantages:
1. the magnetic photocatalyst provided by the invention is prepared from Fe 3 O 4 Consists of small-size CdS and carbon quantum dots, wherein CdS nano particles wrap Fe 3 O 4 The carbon quantum dots are uniformly distributed on the surface of CdS; fe in the synthesis process of the photocatalyst 3 O 4 The surface wrapping of the small-size CdS and the modification of the carbon quantum dots are synchronously performed, so that the preparation process is simplified, and meanwhile, the carbon quantum dots introduced in situ are uniformly distributed on the surface of the CdS nano particles and are firmly combined.
2. In the magnetic photocatalyst provided by the invention, fe 3 O 4 The existence of the CdS not only improves the stability of CdS, but also is convenient to recycle; the carbon quantum dots are beneficial to adsorbing target pollutants in sewage and promoting separation of CdS photon-generated carriers, so that photocatalysis efficiency is improved.
3. The magnetic photocatalyst provided by the invention can be used for preparing a photocatalyst with the concentration of 100mL and 20 mg.L under the conditions of normal temperature and pressure and simulated sunlight irradiation -1 When the catalyst concentration in the aqueous solution of tetracycline hydrochloride is 200 mg.L -1 When the degradation efficiency is 75% in 20min, 84% in 80min, and 70.1% in the fourth cycle test, compared with 18.4% in the fourth cycle test of CdS, the degradation efficiency is good in cycle stability.
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 description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern (XRD) of sample 1 according to the invention;
FIG. 2 is a scanning electron microscope image of sample 1 according to the present invention;
FIG. 3 is a scanning electron microscope image of comparative example 1 according to the present invention;
FIG. 4 is a scanning electron microscope image of comparative example 2 according to the present invention;
FIG. 5 is a transmission electron microscope image (50 nm) of sample 1 according to the present invention;
FIG. 6 is a transmission electron microscope (5 nm) of sample 1 according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a magnetic photocatalyst, which comprises the following preparation steps:
fe is added to 3 O 4 Dispersing the powder in water, adding organic molecules with polyfunctional groups and easy to carbonize, cadmium-containing compounds and sulfur-containing compounds, reacting at a certain temperature to obtain a precipitate, washing and drying the precipitate to obtain Fe 3 O 4 @cds@cqds powder.
Specifically, fe 3 O 4 Dispersing the powder in water, adding organic molecule with multiple easily carbonizable functional groups, cadmium-containing compound and sulfur-containing compound, mixing, reacting at 160-200deg.C for 3-7 hr, cooling to room temperature to obtain precipitate, washing and drying to obtain Fe 3 O 4 @cds@cqds powder.
Specifically, the organic molecule containing polyfunctional groups and being easily carbonized is ascorbic acid or glucose.
Specifically, the organic molecule containing multifunctional groups and easy to carbonize is ascorbic acid; ascorbic acid, cadmium element, fe 3 O 4 The molar ratio of the sulfur elements is as follows: (2-21): (16-24): (20-30): (25-37).
Specifically, fe 3 O 4 When the powder is dispersed in water, fe 3 O 4 The mass ratio of the water to the water is (1-3) 1000。
Specifically, fe 3 O 4 The preparation method of the powder comprises the following steps: dissolving ferric trichloride hexahydrate, trisodium citrate dihydrate and anhydrous sodium acetate in ethylene glycol, mixing, reacting at 180-220 ℃ for 8-12h, cooling to room temperature, collecting precipitate, and drying to obtain Fe 3 O 4 And (3) powder.
Concretely, the mass ratio of ferric trichloride hexahydrate, trisodium citrate dihydrate, anhydrous sodium acetate and ethylene glycol is (9-13): (3-6): (17-25): (310-470).
Specifically, fe 3 O 4 The particle size of the powder is less than or equal to 300nm.
Example 1
Preparation of magnetic photocatalyst (sample 1)
1) Respectively weighing 1.1g of ferric trichloride hexahydrate, 0.5g of trisodium citrate dihydrate and 2.1g of anhydrous sodium acetate, dissolving the ferric trichloride hexahydrate, the trisodium citrate dihydrate and the anhydrous sodium acetate in 35mL of ethylene glycol, mixing, transferring into a reaction vessel, reacting for 10 hours at 200 ℃, cooling to room temperature after the reaction is finished, collecting a precipitate, washing and drying to obtain Fe 3 O 4 Powder;
Fe 3 O 4 the particle size of the powder is less than or equal to 300nm, and Fe in the embodiment 3 O 4 The average particle size of the powder was 150nm.
2) Weigh 60mg of Fe 3 O 4 Powder of Fe 3 O 4 Dispersing the powder in 30mL of water, adding 18.3mg of ascorbic acid (molecular weight is 176.13), 55.3mg of cadmium acetate dihydrate (molecular weight is 266.53) and 23.7mg of thiourea (molecular weight is 76.12), uniformly mixing, adding into a reaction kettle, reacting at 180 ℃ for 5h, cooling to room temperature to obtain a precipitate, washing and drying the precipitate to obtain Fe 3 O 4 The @ CdS @ CQDs powder, sample 1 was labeled Fe 3 O 4 @CdS@0.5CQDs。
Wherein, ascorbic acid, cadmium element and Fe 3 O 4 The molar ratio of the sulfur elements is 10:20:25:31.
Comparative example preparation
Comparative example 1 was prepared by adding 55.3mg of cadmium acetate dihydrate and 23.7mg of thiourea to 30mL of water, uniformly mixing, adding to a reaction kettle, reacting at 180 deg.c for 5 hours, cooling to room temperature to obtain a precipitate, washing and drying the precipitate to obtain catalyst CdS (comparative example 1).
Comparative example 2 preparation 1.1g of ferric trichloride hexahydrate, 0.5g of trisodium citrate dihydrate and 2.1g of anhydrous sodium acetate were weighed, respectively, ferric trichloride hexahydrate, trisodium citrate dihydrate and anhydrous sodium acetate were dissolved in 35mL of ethylene glycol, mixed, transferred into a reaction vessel, reacted at 200℃for 10 hours, cooled to room temperature after the completion of the reaction, and then the precipitate was collected, washed and dried to obtain Fe 3 O 4 Powder (comparative example 2).
Comparative example 3 preparation 1.1g of ferric trichloride hexahydrate, 0.5g of trisodium citrate dihydrate and 2.1g of anhydrous sodium acetate were weighed, respectively, ferric trichloride hexahydrate, trisodium citrate dihydrate and anhydrous sodium acetate were dissolved in 35mL of ethylene glycol, mixed, transferred into a reaction vessel, reacted at 200℃for 10 hours, cooled to room temperature after the completion of the reaction, and then the precipitate was collected, washed and dried to obtain Fe 3 O 4 Powder; weigh 60mg of Fe 3 O 4 Powder of Fe 3 O 4 Dispersing the powder in 30mL water, adding 55.3mg cadmium acetate dihydrate (molecular weight 266.53) and 23.7mg thiourea, mixing, adding into a reaction kettle, reacting at 180deg.C for 5 hr, cooling to room temperature to obtain precipitate, washing and drying to obtain Fe 3 O 4 @ CdS (comparative example 3).
Comparative example 4 preparation in 30mL of water, 18.3mg of ascorbic acid, 55.3mg of cadmium acetate dihydrate (molecular weight 266.53) and 23.7mg of thiourea were added, after mixing uniformly, the mixture was added to a reaction vessel, reacted at 180 c for 5 hours, cooled to room temperature, to obtain a precipitate, washed and dried to obtain cds@cqds powder (comparative example 4).
Sample 1 was analyzed using an X-ray diffractometer (XRD) and a Scanning Electron Microscope (SEM), and fig. 1 is an XRD analysis chart of sample 1; FIG. 2 is a scanning electron microscope image of sample 1; FIG. 3 is a scanning electron microscope image of comparative example 1; FIG. 4 is a scanning electron microscope image of comparative example 2.
FIG. 1 shows that sample 1 contains Fe 3 O 4 And CdS, fe 3 O 4 In the cubic phase crystal system, cdS is a hexagonal phase crystal system, no related diffraction peak of the carbon quantum dots is observed in the sample 1, which indicates that the content of the carbon quantum dots is low, and the diffraction peak of the carbon quantum dots cannot be detected by XRD.
Comparison of fig. 2, 3 and 4 shows that the addition of ascorbic acid can effectively reduce the size of CdS nanoparticles, and that small-sized CdS is encapsulated in Fe 3 O 4 The surface of the particles.
As shown in fig. 5 and 6, sample 1 was analyzed by High Resolution Transmission Electron Microscopy (HRTEM), and Fe of sample 1 was measured 3 O 4 The surface is wrapped by CdS nano particles with small size, the shell layer is thinner, and the carbon quantum dots are modified on the CdS surface, thus proving the successful preparation of the catalyst.
Sewage treatment test
S201) respectively weighing 20mg of sample 1, 20mg of comparative example 2, 20mg of comparative example 3 and 20mg of comparative example 4, respectively, and ultrasonically dispersing in 100mL of tetracycline hydrochloride aqueous solution to form a suspension, and mechanically stirring in a dark room for 0.5h, wherein the tetracycline hydrochloride concentration in the tetracycline hydrochloride aqueous solution is 20mg.L -1
S202) using a 300W Xe lamp as a light source to provide simulated sunlight with a wavelength mainly in the range of 300-780nm, irradiating the surface of the suspension with a maximum optical power density of 200mW cm -2
S203) the solutions prepared in sample 1, comparative example 2, comparative example 3 and comparative example 4 were added to the reaction at a fixed amount, centrifuged, subjected to film-coating treatment, and then tested using an ultraviolet-visible spectroradiometer. Wherein the characteristic absorption wavelength of the tetracycline hydrochloride is 356nm.
As shown in Table 1, the test results show that the pure CdS has poor adsorption capacity to tetracycline hydrochloride, and the CdS@CQDs compared with the pure CdS show that the presence of the carbon quantum dots is favorable for the adsorption of the catalyst to the tetracycline hydrochloride in water, and Fe 3 O 4 The improvement in @ CdS performance was attributed to Fe 3 O 4 Can transfer the photo-generated holes in the CdS, and the photo-generated holes in the CdS can be transferredMove to Fe 3 O 4 On the one hand, the composition with the photo-generated electrons can be restrained, the photo-generated carrier separation efficiency can be improved, and on the other hand, the stability of cadmium sulfide can be improved. Fe (Fe) 3 O 4 The @ CdS @ CQDs show optimal degradation performance, 75% of the initial concentration of tetracycline hydrochloride is degraded in 20min, and 84% is degraded in 80min, indicating Fe 3 O 4 And the carbon quantum dots can synergistically improve the CdS photocatalytic performance.
As shown in Table 2, sample 1 and comparative example 1 were subjected to four photocatalytic cycle reactions (first cycle of 0 to 140min, second cycle of 140 to 280min, third cycle of 280 to 420min, fourth cycle of 420 to 560 min) for recycling Fe, respectively 3 O 4 Light catalytic degradation of tetracycline hydrochloride ((20mg.L) by @ CdS@CQDs compared with pure CdS -1 ) Less performance degradation, indicating Fe 3 O 4 The catalyst @ CdS @ CQDs has good cycling stability.
Example two
The preparation procedure for sample 2 was identical to that for sample 1, except that the amount of ascorbic acid added in step 2 was 3.6mg, sample 2 was labeled Fe 3 O 4 @CdS@0.1CQDs。
The preparation procedure for sample 3 was identical to that for sample 1, except that the amount of ascorbic acid added in step 2 was 10.9mg, and sample 3 was labeled Fe 3 O 4 @CdS@0.3CQDs。
The preparation procedure for sample 4 was identical to that for sample 1, except that the ascorbic acid was added in an amount of 25.6mg in step 2, and comparative example 4 was labeled Fe 3 O 4 @CdS@0.7CQDs。
The preparation procedure for sample 5 was identical to that for sample 1, except that the amount of ascorbic acid added in step 2 was 36.6mg, sample 5 was labeled Fe 3 O 4 @CdS@1.0CQDs。
As shown in table 3, samples 1, 2, 3, 4 and 5 simulate the performance of solar degradation of antibiotics in water, and the results show that samples 1, 2, 3, 4 and 5 have better photocatalytic performance.
Example III
Sample 6 was prepared in the same manner as sample 1, except that 60mgFe was used 3 O 4 Dispersing the powder in 30mL of water, adding 18.3mg of ascorbic acid, 55.3mg of cadmium acetate dihydrate (molecular weight is 266.53) and 23.7mg of thiourea, uniformly mixing, adding into a reaction kettle, reacting for 7h at 160 ℃, cooling to room temperature, washing and drying the precipitate to obtain Fe 3 O 4 The @ CdS @ CQDs powder, sample 6.
Sample 7 was identical to sample 1 in preparation except that 60mgFe was used 3 O 4 Dispersing the powder in 30mL of water, adding 18.3mg of ascorbic acid, 55.3mg of cadmium acetate dihydrate (molecular weight is 266.53) and 23.7mg of thiourea, uniformly mixing, adding into a reaction kettle, reacting for 3h at 200 ℃, cooling to room temperature, washing and drying the precipitate to obtain Fe 3 O 4 The @ CdS @ CQDs powder, sample 7.
Sample 8 was identical to sample 1 in preparation steps, except that Fe was obtained 3 O 4 In the powder process, the reaction temperature is 180 ℃ for 12 hours.
Sample 9 was identical to sample 1 in preparation steps, except that Fe was obtained 3 O 4 In the powder process, the reaction temperature is 220 ℃ for 8 hours.
Sample 10 was prepared in the same manner as sample 1, except that the organic molecule having a polyfunctional group which is easily carbonized was glucose.
The performance test of the photocatalyst for degrading antibiotics in water under simulated sunlight is carried out on samples 6 to 10, and the test results are shown in table 4.
As can be seen from Table 4, fe is prepared by reacting glucose as an organic molecule which is easily carbonized and contains a polyfunctional group at a predetermined reaction temperature and reaction time 3 O 4 The @ CdS @ CQDs powder has good photocatalytic performance.
Example IV
Sample 11 was prepared in the same manner as sample 1, except that ascorbic acid, cadmium element, fe 3 O 4 And the molar ratio of sulfur elements is 8:16:20:25.
Sample 12 was prepared in the same manner as sample 1, except that ascorbic acid, cadmium element, fe 3 O 4 And the molar ratio of sulfur elements is 12:24:30:37.
The performance of the photocatalyst in degrading antibiotics in water under simulated sunlight was tested on samples 11 and 12, and the test results are shown in table 5. As can be seen from Table 5, fe was produced in a predetermined molar ratio range 3 O 4 The @ CdS @ CQDs powder has good photocatalytic performance.
Table 1 performance of photocatalyst in degrading antibiotics in water under simulated sunlight
Table 2 cycling stability of photocatalyst to degrade antibiotics in water under simulated sunlight
TABLE 3 Property of photocatalyst to degrade antibiotics in Water under simulated sunlight
Table 4 performance of photocatalyst in degrading antibiotics in water under simulated sunlight
TABLE 5 Property of photocatalyst to degrade antibiotics in Water under simulated sunlight
A period of-60 min in Table 1 represents the very beginning of the darkroomThe method comprises the steps of carrying out a first treatment on the surface of the 0min represents a darkroom for 60min; the positive value time represents the illumination time; c (C) t Is the concentration detected in real time, C 0 Is the initial concentration. Tables 2, 3, 4 and 5, C t Is the concentration detected in real time, C 0 Is the initial concentration.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (3)

1. An application of a magnetic photocatalyst in sewage treatment is characterized in that: the preparation method comprises the following preparation steps:
fe is added to 3 O 4 Dispersing the powder in water, adding ascorbic acid, cadmium-containing compound and sulfur-containing compound, mixing, reacting at 160-200deg.C for 3-7 hr, cooling to room temperature to obtain precipitate, washing and drying to obtain Fe 3 O 4 @cds@cqds powder;
the ascorbic acid, cadmium element and Fe 3 O 4 The molar ratio of the sulfur elements is as follows: (2-21): (16-24): (20-30): (25-37);
the Fe is 3 O 4 When the powder is dispersed in water, the Fe 3 O 4 The mass ratio of the water to the water is (1-3) 1000;
the Fe is 3 O 4 The preparation method of the powder comprises the following steps: dissolving ferric trichloride hexahydrate, trisodium citrate dihydrate and anhydrous sodium acetate in ethylene glycol, mixing, reacting for 8-12h at 180-220 ℃, cooling to room temperature, collecting precipitate, and drying to obtain Fe 3 O 4 Powder;
the mass ratio of the ferric trichloride hexahydrate to the trisodium citrate dihydrate to the anhydrous sodium acetate to the ethylene glycol is (9-13): (3-6): (17-25): (310-470).
2. Use of a magnetic photocatalyst according to claim 1 in the treatment of sewage, characterized in that: the Fe is 3 O 4 The particle size of the powder is less than or equal to 300nm.
3. Use of a magnetic photocatalyst according to any one of claims 1-2 in sewage treatment, characterized in that: the magnetic photocatalyst comprises Fe 3 O 4 Powder of Fe 3 O 4 The powder is coated with CdS, and the carbon quantum dots are uniformly distributed on the surface of the CdS.
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