CN115414949A - Magnetic popcorn-shaped CuS/Fe with high electron transfer rate and easy recovery 3 O 4 Preparation method and application of catalyst - Google Patents
Magnetic popcorn-shaped CuS/Fe with high electron transfer rate and easy recovery 3 O 4 Preparation method and application of catalyst Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/50—
-
- 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
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- 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
A preparation method and application of a magnetic popcorn chicken-shaped CuS/Fe3O4 catalyst with high electron transfer rate and easy recovery relate to the field of water treatment materials. The invention aims to solve the problem of the existing Fe 3 O 4 Surface Fe 3+ /Fe 2+ Slow cycle conversion, fe 3+ Accumulation of Fe 3 O 4 Easy agglomeration of nano particles, low catalytic activity of flaky CuS, difficult recovery and the likeProblem to realize Fe 3 O 4 Surface Fe 3+ /Fe 2+ The rapid circulation of the catalyst is established, and the popcorn-shaped catalyst CuS/Fe is established 3 O 4 A preparation method. The method comprises the following steps: 1. preparing a solution A; 2. preparation of Fe 3 O 4 A precursor; 3. obtaining Fe by solvothermal reaction 3 O 4 (ii) a 4. Washing and drying; 5. preparing a solution B; 6. preparing a mixed solution C; 7. preparation of CuS/Fe 3 O 4 A precursor; 8. the thermal reaction of the solvent is carried out to obtain CuS/Fe 3 O 4 (ii) a 9. And (5) washing and drying. Prepared CuS/Fe 3 O 4 The catalyst activates persulfate to treat the dye wastewater. The advantages are that: fe 3 O 4 The nano particles have good dispersibility on the CuS flower-shaped nano sheet, large specific surface area, good magnetism and Fe 3 O 4 Surface Fe 3+ /Fe 2+ The method has the advantages of rapid circulation, remarkable effect of activating persulfate to degrade methyl orange wastewater and wide prospect.
Description
Technical Field
The invention relates to the field of water treatment materials, in particular to a magnetic popcorn chicken catalyst CuS/Fe with high electron transfer rate and easy recovery 3 O 4 The preparation method and the application thereof.
Background
Azo dyes are generally used as coloring agents in the industries of printing, spinning, chemical engineering, food processing and the like, and a large amount of generated dye wastewater is discharged into a water environment, so that the light transmittance of a water body is reduced, the photosynthesis of aquatic plants is influenced, and the health of human beings is endangered. The traditional wastewater treatment methods, such as coagulation, precipitation, filtration and other technologies, relate to the problems of regeneration and replacement of materials, sludge treatment and the like, the wastewater treatment efficiency is low, and the development of an effective method for degrading azo dyes remained in water is urgently needed.
The advanced oxidation technology based on sulfate radicals is simple and efficient to operate, can rapidly decompose most of pollutants difficult to degrade, and shows great advantages and application potential in the aspect of dye wastewater treatment. Iron-based catalyst (e.g. Fe) 2 O 3 、Fe 3 O 4 FeOOH, etc.) is environmentally friendly, inexpensive, readily available, and compared to other iron-based catalysts, fe 3 O 4 Containing Fe at the same time 2+ And Fe 3+ The compound has an inverse spinel structure, can provide a transfer space for electrons, is easy to synthesize and realize solid-liquid separation, and is often used for activating persulfate to degrade organic pollutants. However, in the process of activating persulfate, fe of the surface thereof 2+ Is easy to be oxidized into Fe 3+ Is continuously consumed, resulting in Fe 3 O 4 The efficiency of activating persulfate is low. Therefore, how to increase Fe 3+ Conversion to Fe 2+ The efficiency of (2) is a difficult problem to be solved urgently. At present, for accelerating Fe 3+ Reduction to Fe 2+ The method mainly comprises the following steps:
coupled with optical, electrical, etc. techniques. Using electrons provided by electrochemical reaction or photo-generated electrons to convert Fe 3+ Conversion to Fe 2+ However, optical and electrical instruments and equipment are required, the process is complex, and the operation cost is high.
A reducing agent is added. Such as hydroxylamineHA. Direct electron supply of sodium sulfite and sodium thiosulfate to accelerate Fe 2+ Regeneration of (1), reduction of Fe 3+ Accumulation of (2). The method is simple to operate, but has the problems that the reducing agent and pollutants compete for free radicals, the reducing agent is difficult to recover, and the recycling rate is low.
And a low-valent metal (Cu) 0 、Cu + And Mn 3+ Etc.) are combined. By means of low-valence metals and Fe 3+ Fe accelerated by electron transfer therebetween 3+ The reduction and electron transfer process occurs in the catalyst, the reaction rate is high, and the organic matter degradation efficiency is high. However, regeneration and recovery of low-priced metals are difficult. Further, fe having a ferromagnetic property 3 O 4 The agglomeration of the nanoparticles inevitably occurs, and the specific surface area is reduced, resulting in a decrease in catalytic activity.
Copper sulfide (CuS) has good electrical conductivity, mechanical stability and thermal stability, and is often used to activate persulfate to degrade organic pollutants. Sulfur (e.g., S) on the surface of CuS as compared to conventional metal oxide catalysts 2- And S n 2- ) The regeneration of the metal active sites can be realized through electron transfer, and the activation of persulfate and the degradation of pollutants are enhanced. However, the flaky CuS has a small specific surface area, low catalytic activity, and is difficult to separate and recover.
Thus, fe 3 O 4 And CuS catalysts need further improvement and enhancement.
In the invention, fe 3 O 4 The nano particles are fixed on the surface of the flaky CuS to prepare the magnetic popcorn chicken-shaped CuS/Fe which has high electron transfer rate and is easy to recycle 3 O 4 Catalyst, overcome Fe 3 O 4 Agglomeration of the nanoparticles; fe is realized by utilizing good electron transfer capability of low-valence sulfur on the surface of CuS 2+ Regeneration of (1), increase of Fe 3 O 4 The catalytic activity of (a); using Fe 3 O 4 The introduction of the nano particles endows CuS with magnetism, increases the specific surface area of CuS, and provides more active sites for the degradation of pollutants. The catalyst has simple preparation process, low cost and high catalytic activityHigh in performance, easy to separate and recover and has great application potential.
Disclosure of Invention
In view of the deficiencies of the above catalysts, the object of the present invention is to solve the existing Fe 3 O 4 Surface Fe 3+ /Fe 2+ Slow conversion and Fe 3+ Large amount of accumulated Fe in the reaction process 3 O 4 The problems of easy agglomeration of nano particles, low flaky CuS catalytic activity and difficult recovery are solved, and the magnetic popcorn-shaped CuS/Fe with high electron transfer rate and easy recovery is provided 3 O 4 A preparation method and application of the catalyst.
The magnetic popcorn chicken catalyst with fast electron transfer rate and easy recovery has the chemical formula of CuS/Fe 3 O 4 ；Fe 3 O 4 The nano particles are loaded on the nano sheet with the CuS flower-shaped structure and are in a popcorn chicken shape.
Magnetic popcorn chicken-shaped catalyst CuS/Fe with high electron transfer rate and easy recovery 3 O 4 The preparation method comprises the following steps:
1. preparation of solution a: dissolving ferric chloride and sodium citrate in ethylene glycol, and stirring at 40 deg.C until ferric chloride and sodium citrate are completely dissolved to obtain solution A.
2. Preparation of Fe 3 O 4 Precursor: adding sodium acetate into the solution A, and continuously stirring at the temperature of 40 ℃ until the solution is clear to obtain Fe 3 O 4 And (3) precursor.
3. Solvent thermal reaction: mixing Fe 3 O 4 And placing the precursor in a reaction kettle lined with polytetrafluoroethylene to carry out solvothermal reaction to obtain a solvothermal reaction product.
4. Washing and drying: taking out the solvothermal reaction product, washing and drying to obtain the magnetic nano-particle Fe 3 O 4 。
5. Preparation of solution B: dissolving copper chloride in ethylene glycol, and stirring at the temperature of 30 ℃ until the copper chloride is completely dissolved to obtain a solution B.
6. Preparing a mixed solution C: fe prepared as above 3 O 4 Adding the mixture into the solution B, and adding the mixture into the solution B,stirring and mixing evenly to obtain a mixed solution C.
7. Preparation of CuS/Fe 3 O 4 Precursor: adding thiourea into the mixed solution C, and continuously stirring at the temperature of 30 ℃ until the thiourea is completely dissolved to obtain CuS/Fe 3 O 4 And (3) precursor.
8. Solvent thermal reaction: mixing CuS/Fe 3 O 4 And placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction to obtain a solvothermal reaction product.
9. Washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the CuS/Fe in the shape of popcorn chicken 3 O 4 A catalyst.
The magnetic popcorn chicken-shaped CuS/Fe has high electron transfer rate and is easy to recover 3 O 4 The application of the catalyst lies in utilizing CuS/Fe 3 O 4 Used as a catalyst to activate persulfate to treat dye wastewater.
The invention has the advantages that:
1. magnetic popcorn-shaped CuS/Fe is prepared by adopting a solvothermal method 3 O 4 Catalyst with CuS catalyst or Fe alone 3 O 4 Compared with the catalyst, the catalyst promotes the activation of PS and the degradation of pollutants under the synergistic action of bimetal, and the low-valence sulfur on the surface of CuS provides electrons to accelerate Fe 3+ /Fe 2+ Circulation of (2), reduction of Fe 3 O 4 Surface Fe 3+ The accumulation of (b) contributes to the improvement of catalytic performance.
2. Magnetic CuS/Fe prepared by the invention 3 O 4 The catalyst is in a popcorn shape, so that the specific surface area of the catalyst is greatly increased, and the adsorption of pollutants and the activation of persulfate are facilitated.
3. Magnetic CuS/Fe prepared by the invention 3 O 4 The catalyst is in the shape of popcorn of chicken, and is magnetic Fe 3 O 4 The nano particles are loaded on the nano sheet with the CuS flower-shaped structure, which is beneficial to Fe 3 O 4 The nano particles are dispersed to avoid agglomeration.
4. Magnetic CuS/Fe prepared by the invention 3 O 4 The catalyst is in the shape of popcorn chicken and is magnetic Fe 3 O 4 The nano particles are loaded on the nano sheet with the CuS flower-shaped structure, so that the specific surface area of the CuS is increased, more active sites are provided for the degradation of pollutants, the CuS is endowed with magnetism, the separation and recovery are facilitated, and the loss is prevented.
5. The invention adopts thiourea as a sulfur source, ethylene glycol as a solvent, and copper ions, thiourea and ethylene glycol form a chelate [ Cu (CH) 4 N 2 S)m(C 2 H 6 O 2 )n] 2+ The release rate of the sulfur ions in the reaction process is controlled, the concentration of the sulfur ions is greatly reduced, and meanwhile, hexagonal phase copper sulfide crystals grow anisotropically to obtain the flower-shaped structure CuS formed by the nanosheets.
Fe in the catalyst prepared by the invention 3 O 4 The nanoparticles have good dispersibility, high electron transfer rate and strong magnetism, and the effect of activating persulfate to degrade methyl orange wastewater is obvious (under the conditions that the initial pH is 7, the adding amount of the catalyst is 0.4g/L and the concentration of the persulfate is 3mmol/L, when the concentration of the methyl orange is 25mg/L, the removal rate of the methyl orange can reach 94 percent after the reaction is carried out for 30 min), the method is easy to separate and recycle, and can be applied to dye wastewater treatment.
Drawings
FIG. 1 is the magnetic popcorn chicken-shaped CuS/Fe obtained in example 1 3 O 4 Scanning electron micrographs of the catalyst.
FIG. 2 is the magnetic popcorn chicken-shaped CuS/Fe obtained in example 1 3 O 4 XRD pattern of the catalyst.
FIG. 3 shows the magnetic popcorn chicken-shaped CuS/Fe obtained in example 1 3 O 4 Hysteresis loop of the catalyst at room temperature.
FIG. 4 shows the magnetic popcorn chicken-shaped CuS/Fe obtained in example 1 3 O 4 XPS spectrum of catalyst Fe element.
FIG. 5 is the magnetic popcorn chicken-shaped CuS/Fe obtained in example 1 3 O 4 XPS spectrum of catalyst S element.
FIG. 6 is a degradation curve of methyl orange wastewater, wherein diamond-solid in the graph represents the degradation curve of the methyl orange wastewater obtained in example 2, T X T represents the degradation curve of the methyl orange wastewater obtained in comparative example 3, A represents the degradation curve of the methyl orange wastewater obtained in comparative example 4, and 9632represents the degradation curve of the methyl orange wastewater obtained in comparative example 5.
Detailed Description
The first embodiment is as follows: the embodiment is to prepare the magnetic popcorn-shaped catalyst with high electron transfer rate and easy recovery, and the chemical formula of the catalyst is CuS/Fe 3 O 4 ，Fe 3 O 4 The nanoparticles are loaded on the nanosheets of the CuS flower-like structure.
The low-valence sulfur on the surface of the magnetic popcorn chicken catalyst prepared by the embodiment provides electrons to accelerate Fe 3+ /Fe 2+ Circulation of (2), reduction of Fe 3 O 4 Surface Fe 3+ The accumulation of (2) is beneficial to electron transfer in the catalytic reaction process, thereby improving the catalytic performance and overcoming Fe 3 O 4 Agglomeration of the nanoparticles; fe 3 O 4 The nano particles endow CuS with magnetism, the prepared catalyst is easy to separate and recover, and the specific surface area of CuS is increased, so that more active sites are provided for the degradation of pollutants.
The second embodiment is as follows: the embodiment provides a magnetic popcorn chicken-shaped catalyst CuS/Fe with fast electron transfer rate and easy recovery 3 O 4 The preparation method comprises the following steps:
1. preparation of solution A: dissolving ferric chloride and sodium citrate in ethylene glycol, and stirring at 40 ℃ until the ferric chloride and the sodium citrate are completely dissolved to obtain a solution A;
2. preparation of Fe 3 O 4 Precursor: adding sodium acetate into the solution A, and continuously stirring at the temperature of 40 ℃ until the solution is clear to obtain Fe 3 O 4 A precursor;
3. solvent thermal reaction: mixing Fe 3 O 4 Placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction to obtain a solvothermal reaction product;
4. washing and drying: taking out the solvothermal reaction product, washing and drying to obtain the magnetic nano-particle Fe 3 O 4 ；
5. Preparation of solution B: dissolving copper chloride in ethylene glycol, and stirring at the temperature of 30 ℃ until the copper chloride is completely dissolved to obtain a solution B;
6. preparing a mixed solution C: fe prepared as above 3 O 4 Adding the mixture into the solution B, stirring and uniformly mixing to obtain a mixed solution C;
7. preparation of CuS/Fe 3 O 4 Precursor: adding thiourea into the mixed solution C, and continuously stirring at the temperature of 30 ℃ until the thiourea is completely dissolved to obtain CuS/Fe 3 O 4 A precursor;
8. carrying out solvothermal reaction: mixing CuS/Fe 3 O 4 Placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction to obtain a solvothermal reaction product;
9. washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the magnetic popcorn-shaped CuS/Fe 3 O 4 A catalyst.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: in the first step, the volume ratio of the ferric chloride substance to the glycol is 5mmol to 30mL, and the mass of the sodium citrate is 0.8 g. The rest is the same as the second embodiment.
The fourth concrete implementation mode is as follows: the present embodiment differs from the second or third embodiment in that: and in the second step, the ratio of the amount of the ferric chloride substance to the amount of the sodium acetate substance is 1: 8.8. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode is as follows: the present embodiment differs from the second to fourth embodiments in that: in the third step, the solvothermal reaction temperature is 200 ℃, the solvothermal time is 10 hours, and the filling degree of the polytetrafluoroethylene-lined reaction kettle is 60-70%. The other points are the same as those in the second to fourth embodiments.
The sixth specific implementation mode is as follows: the second to fifth embodiments are different from the first to fifth embodiments in that: and step four, alternately washing the mixture for 3 times by adopting ethanol and deionized water. The rest is the same as the second to fifth embodiments.
The seventh concrete implementation mode: the present embodiment differs from the second to sixth embodiments in that: the drying process in the fourth step is drying for 8-10 h at the temperature of 60 ℃. The rest is the same as the second to sixth embodiments.
The specific implementation mode is eight: the second to seventh embodiments are different from the first to seventh embodiments in that: and in the step five, the volume ratio of the copper chloride substance to the ethylene glycol is 1.5mmol. The rest is the same as the second to seventh embodiments.
The specific implementation method nine: the present embodiment is different from the second to eighth embodiments in that: in step six, fe 3 O 4 The mass of (3) was 0.144g. The rest is the same as the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment is different from the second to ninth embodiments in that: and the ratio of the amount of the copper chloride substance to the amount of the thiourea substance in the seventh step is 1. The rest is the same as the second to ninth embodiments.
The concrete implementation mode eleven: the present embodiment differs from the second to tenth embodiments in that: and step eight, the solvothermal reaction temperature is 180 ℃, the solvothermal time is 2 hours, and the filling degree of the reaction kettle lined with polytetrafluoroethylene is 60-70%. The others are the same as the second to tenth embodiments.
The specific implementation mode twelve: the present embodiment differs from the second to eleventh embodiments in that: and in the ninth step, the washing is performed for 3 times by adopting ethanol and deionized water alternately. The others are the same as in the second to eleventh embodiments.
The specific implementation mode thirteen: the second to twelfth differences from the present embodiment are as follows: and the drying process in the step nine is vacuum drying for 8-10 h at the temperature of 60 ℃. The rest is the same as the second to twelfth embodiments.
The specific implementation mode fourteen are as follows: the embodiment is the magnetic popcorn chicken-shaped CuS/Fe with fast electron transfer rate and easy recovery 3 O 4 Use of a catalyst, characterized by magnetic popcorn-like CuS/Fe 3 O 4 Used as a catalyst to activate persulfate to treat dye wastewater.
The concrete implementation mode is fifteen: the present embodiment is different from the fourteenth embodiment in that: the dye wastewater is methyl orange wastewater. The rest is the same as the fourteenth embodiment.
The inventive content is not limited to the embodiments described above, wherein one or a combination of several embodiments may equally fulfill the objects of the invention.
The following experiments are adopted to verify the effect of the invention:
example 1: magnetic popcorn chicken-shaped catalyst CuS/Fe with high electron transfer rate and easy recovery 3 O 4 The preparation method comprises the following steps:
1. preparation of solution a: dissolving 5mmol of ferric chloride and 0.8g of sodium citrate in 30mL of glycol, and stirring at 40 ℃ for 5-7 h until the ferric chloride and the sodium citrate are completely dissolved to obtain a solution A.
2. Preparation of Fe 3 O 4 Precursor: adding 3.6g of sodium acetate into the solution A, and continuously stirring for 1h at the temperature of 40 ℃ until the solution is clear to obtain Fe 3 O 4 And (3) precursor.
3. Solvent thermal reaction: mixing Fe 3 O 4 And placing the precursor into a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL, and obtaining a solvothermal reaction product.
4. Washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the magnetic nano-particle Fe 3 O 4 。
5. Preparation of solution B: dissolving 1.5 mmol/L copper chloride in 30mL ethylene glycol, and stirring at 30 deg.C for 30min until the copper chloride is completely dissolved to obtain solution B.
6. Preparing a mixed solution C: 0.144g of Fe prepared above 3 O 4 And adding the mixture into the solution B, stirring and uniformly mixing to obtain a mixed solution C.
7. Preparation of CuS/Fe 3 O 4 Precursor: adding 0.228g of thiourea into the mixed solution C, and continuously stirring for 1h at the temperature of 30 ℃ until the thiourea is completely dissolved to obtain CuS/Fe 3 O 4 And (3) precursor.
8. Carrying out solvothermal reaction: mixing CuS/Fe 3 O 4 Placing the precursor in the polytetrafluoroethylene liningAnd carrying out solvothermal reaction in an ethylene reaction kettle, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL, so as to obtain a solvothermal reaction product.
9. Washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the magnetic popcorn-shaped CuS/Fe 3 O 4 A catalyst.
The operating parameters for the solvothermal reaction described in step four of example 1 are as follows: the solvothermal temperature is 200 ℃ and the solvothermal time is 10h.
The washing procedure described in example 1, step five is as follows: and (3) alternately washing by using ethanol and deionized water for 3 times.
The drying process described in example 1, step five was as follows: drying at 60 deg.C for 10h.
The operating parameters for the solvothermal reaction described in step eight of example 1 are as follows: the solvothermal temperature is 180 ℃, and the solvothermal time is 2 hours.
The washing procedure described in example 1, step nine is as follows: and (3) alternately washing by using ethanol and deionized water for 3 times.
Example 1 step nine the drying procedure is as follows: drying under vacuum at 60 deg.C for 10h.
Comparative example 1: fe 3 O 4 The preparation method of the catalyst is specifically completed according to the following steps:
1. dissolving 5mmol/L ferric chloride and 0.8g sodium citrate in 30mL ethylene glycol, and stirring at 40 ℃ for 5-7 h until the ferric chloride and the sodium citrate are completely dissolved to obtain a solution A;
2. adding 3.6g of sodium acetate into the solution A, and continuously stirring for 1h at the temperature of 40 ℃ until the solution is clear to obtain Fe 3 O 4 A precursor;
3. mixing Fe 3 O 4 Placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL under the conditions that the solvothermal temperature is 200 ℃ and the solvothermal time is 10 hours, so as to obtain a solvothermal reaction product;
4. washing and drying: taking out the solvent thermal reaction product, washing and dryingTo obtain magnetic nano-particle Fe 3 O 4 ；
Comparative example 1 the washing procedure described in step four was as follows: and alternately washing with ethanol and deionized water for 3 times.
Comparative example 1 the drying process in step four is as follows: drying at 60 deg.C for 10 hr.
Comparative example 2: the preparation method of the CuS catalyst is specifically completed according to the following steps:
1. dissolving 1.5 mmol/L copper chloride in 30mL ethylene glycol, and stirring at 30 ℃ for 30min until the copper chloride is completely dissolved to obtain a solution A;
2. adding 0.228g of thiourea into the solution A obtained in the step one, and continuously stirring for 1h at the temperature of 30 ℃ until the thiourea is completely dissolved to obtain a CuS precursor;
3. placing the CuS precursor into a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction, wherein the volume of the reaction kettle lined with polytetrafluoroethylene is 50mL under the conditions that the solvothermal temperature is 180 ℃ and the solvothermal time is 2 hours, so as to obtain a solvothermal reaction product;
4. and taking out the solvothermal reaction product, washing and drying to obtain the CuS catalyst.
Comparative example 2 the washing procedure described in step four is as follows: and (3) alternately washing by using ethanol and deionized water for 3 times.
Comparative example 2 the drying process described in step four was as follows: drying at 60 deg.C for 10h.
Magnetic popcorn-like CuS/Fe prepared in example 1 3 O 4 The catalyst was subjected to a scanning electron microscope test, as shown in FIG. 1 (c), cuS/Fe 3 O 4 The nano particles are attached to flower-shaped microspheres assembled by the nano sheets and are in a popcorn shape, and the structure is favorable for adsorbing pollutants and oxidants and exposing more active centers. Scanning Electron micrograph of comparative example 1, as shown in FIG. 1 (a), fe 3 O 4 The particles are spherical particles, the size is uniform, the diameters of the particles are distributed between 100 nm and 200nm, and the particles are slightly agglomerated. In the scanning electron micrograph of comparative example 2, as shown in FIG. 1 (b), cuS is in the form of flower-like microspherical surface of the nanosheet stackSmooth, each nanosheet is about 20-60 nm in thickness, and the special structure is Fe 3 O 4 The attachment of the nanoparticles provides sufficient sites.
Magnetic popcorn-like CuS/Fe prepared in example 1 3 O 4 XRD spectrogram of the catalyst, as shown in figure 2, XRD diffraction peak and Fe of the catalyst 3 O 4 The PDF standard card (PDF # 79-0419) is matched with the PDF standard card (PDF # 78-0876) of the CuS, and the Fe can be known by combining the test result of a scanning electron microscope 3 O 4 Successfully loaded on CuS.
FIG. 3 shows CuS/Fe 3 O 4 Hysteresis loop measured at room temperature. CuS/Fe 3 O 4 The magnetic material has superparamagnetism, the remanence is close to 0, and the maximum saturation magnetization of the magnetic material is 21.7emu/g, so that the magnetic material is favorable for recycling.
Magnetic popcorn-like CuS/Fe obtained in example 1 3 O 4 The catalyst was analyzed by XPS for Fe and S elements. FIG. 4 is an XPS spectrum of Fe element, and FIG. 4 (A) shows magnetic popcorn-like CuS/Fe obtained in example 1 3 O 4 XPS spectrum of Fe element before catalyst reaction, FIG. 4 (B) shows magnetic popcorn-like CuS/Fe obtained in example 1 3 O 4 XPS spectrum of Fe element after catalyst reaction. CuS/Fe 3 O 4 Fe before catalyst reaction 2+ And Fe 3+ The proportions of (A) are 48.4% and 51.6%, respectively; after reaction of the catalyst, fe 3+ The proportion of (C) is reduced to 49.2%, fe 2+ The ratio of (B) is increased to 50.8%, which indicates that CuS/Fe 3 O 4 Fe of the surface 3+ →Fe 2+ Electron transfer occurs. FIG. 5 is an XPS spectrum of the S element, and FIG. 5 (A) shows magnetic popcorn-like CuS/Fe obtained in example 1 3 O 4 XPS spectrum of S element before catalyst reaction, FIG. 5 (B) shows magnetic popcorn-like CuS/Fe obtained in example 1 3 O 4 XPS spectrum of S element, cuS/Fe after catalyst reaction 3 O 4 S before catalyst reaction 2- 、S n 2- 、S 0 、SO 4 2- The proportions of (A) are respectively 44.1%, 40.2%, 11.4% and 4.2%; after the catalyst reaction, S 2- Is reduced to33.9%，S n 2- The relative content of (A) is reduced to 33.4%, S 0 The ratio of (A) is increased to 21.4%, SO 4 2- The ratio of (B) is increased to 11.3%, indicating that CuS/Fe 3 O 4 The low valence sulfur on the surface provides electrons to promote Fe 3+ /Fe 2+ Cycle of (2), reducing Fe 3+ The accumulation of (b) contributes to the improvement of catalytic performance.
Example 2: magnetic popcorn chicken-shaped catalyst CuS/Fe with high electron transfer rate and easy recovery 3 O 4 The magnetic popcorn-like CuS/Fe 3 O 4 Activating persulfate as a catalyst to treat dye wastewater: the dye wastewater is methyl orange wastewater, and the magnetic popcorn-shaped CuS/Fe 3 O 4 The catalyst is the magnetic popcorn-shaped CuS/Fe prepared in example 1 3 O 4 The catalyst is implemented as follows:
1. 150mL of methyl orange wastewater with the concentration of 25mg/L is placed in a 200mL glass beaker, and 3mmol/L persulfate and 0.4g/L of magnetic popcorn-shaped CuS/Fe are added simultaneously 3 O 4 A catalyst.
2. Continuously carrying out catalytic degradation for 30min, sampling 4mL every 5min, immediately adding 0.4mL of methanol, filtering by a 22-micron filter membrane, detecting the concentration of the residual methyl orange in the wastewater at 465nm by adopting an ultraviolet-visible spectrophotometry method, drawing a methyl orange wastewater degradation curve according to detected data, and calculating the removal rate.
Comparative example 3: the comparative example differs from example 2 in that: using Fe 3 O 4 Catalyst replaces magnetic popcorn-shaped CuS/Fe 3 O 4 A catalyst. The rest is the same as in example 2.
Comparative example 4: the comparative example differs from example 2 in that: cuS catalyst is adopted to replace magnetic popcorn-shaped CuS/Fe 3 O 4 A catalyst. The rest was the same as in example 2.
Comparative example 5: the comparative example is different from example 2 in that: no catalyst is used, persulfate is used alone. The rest is the same as in example 2.
Summarizing the degradation curves of the methyl orange wastewater obtained in example 2 and comparative examples 3 to 5FIG. 6 is a graph showing the degradation curve of methyl orange wastewater, wherein diamond-solid in the graph shows the degradation curve of methyl orange wastewater obtained in example 4, wherein a t, x in the graph shows the degradation curve of methyl orange wastewater obtained in comparative example 3, wherein a-solidup in the graph shows the degradation curve of methyl orange wastewater obtained in comparative example 4, wherein a 9632in the graph shows the degradation curve of methyl orange wastewater obtained in comparative example 5; fig. 6 shows that the removal rate of methyl orange after 30min of catalytic degradation in example 4 reaches 94%, the removal rate of methyl orange after 30min of catalytic degradation in comparative example 3 is 55.5%, the removal rate of methyl orange after 30min of catalytic degradation in comparative example 4 is 62%, and the removal rate of methyl orange after 30min of catalytic degradation in comparative example 5 is 42.7%. As can be seen from FIG. 6, example 1 produces CuS/Fe with magnetic flower-like structure compared to PS alone 3 O 4 The efficiency of catalytic degradation of methyl orange is improved by 51.3 percent. The above results indicate CuS/Fe 3 O 4 Can effectively activate PS to degrade methyl orange, cuS/Fe 3 O 4 The catalytic activity of the catalyst is far higher than that of CuS and Fe 3 O 4 . The magnetic popcorn chicken shaped catalyst CuS/Fe obtained by the invention 3 O 4 Low cost, large specific surface area, high catalytic activity, easy separation and recovery and wide application prospect.
Claims (15)
1. Magnetic popcorn chicken-shaped catalyst CuS/Fe with high electron transfer rate and easy recovery 3 O 4 Characterized in that the popcorn chicken catalyst has the chemical formula of CuS/Fe 3 O 4 ，Fe 3 O 4 The nano particles are loaded on the nano sheet with the CuS flower-shaped structure, the catalyst is magnetic and has a popcorn shape, and Fe is realized 3 O 4 Surface Fe 3+ /Fe 2+ The rapid circulation of the Fe is effectively solved 3 O 4 Easy agglomeration of particles, low catalytic activity of flaky CuS and difficult recovery.
2. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 1 3 O 4 The preparation method is characterized by comprising the following steps:
1. preparation of solution a: dissolving ferric chloride and sodium citrate in ethylene glycol, and stirring at 40 ℃ until the ferric chloride and the sodium citrate are completely dissolved to obtain a solution A;
2. preparation of Fe 3 O 4 Precursor: adding sodium acetate into the solution A, and continuously stirring at the temperature of 40 ℃ until the solution is clear to obtain Fe 3 O 4 A precursor;
3. carrying out solvothermal reaction: mixing Fe 3 O 4 Placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction to obtain a solvothermal reaction product;
4. washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the magnetic nano-particle Fe 3 O 4 ；
5. Preparation of solution B: dissolving copper chloride in ethylene glycol, and stirring at the temperature of 30 ℃ until the copper chloride is completely dissolved to obtain a solution B;
6. preparing a mixed solution C: fe prepared as above 3 O 4 Adding the mixture into the solution B, stirring and uniformly mixing to obtain a mixed solution C;
7. preparation of CuS/Fe 3 O 4 Precursor: adding thiourea into the mixed solution C, and continuously stirring at the temperature of 30 ℃ until the thiourea is completely dissolved to obtain CuS/Fe 3 O 4 A precursor;
8. carrying out solvothermal reaction: mixing CuS/Fe 3 O 4 Placing the precursor in a reaction kettle lined with polytetrafluoroethylene for solvothermal reaction to obtain a solvothermal reaction product;
9. washing and drying: taking out the solvent thermal reaction product, washing and drying to obtain the magnetic popcorn-shaped CuS/Fe 3 O 4 A catalyst.
3. The fast electron transfer rate, easily recoverable magnetic popcorn CuS/Fe of claim 2 3 O 4 The preparation method of the catalyst is characterized in that the volume ratio of the amount of the ferric chloride substance to the ethylene glycol in the step one is 5mmol/30mL, and the mass of the sodium citrate is 0.8 g.
4. According to claimThe magnetic popcorn chicken catalyst CuS/Fe with fast electron transfer rate and easy recovery as stated in claim 3 is required 3 O 4 The preparation method is characterized in that the ratio of the amount of the ferric chloride substance to the amount of the sodium acetate substance in the step two is 1: 8.8.
5. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 4 3 O 4 The preparation method is characterized in that the operation parameters of the solvothermal reaction in the third step are as follows: the solvothermal temperature is 200 ℃, the solvothermal time is 10 hours, and the filling degree of the reaction kettle lined with polytetrafluoroethylene is 60-70%.
6. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 5 3 O 4 The preparation method is characterized in that the washing process in the step four is as follows: and alternately washing with ethanol and deionized water for 3 times.
7. The fast electron transfer rate, easily recoverable magnetic popcorn chicken catalyst CuS/Fe of claim 6 3 O 4 The preparation method is characterized in that the drying process in the fourth step is as follows: drying for 8-10 h at 60 ℃.
8. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 7 3 O 4 The preparation method of (1), wherein the volume ratio of the copper chloride substance to the ethylene glycol in the step (five) is 1.5mmol.
9. The fast electron transfer rate, easily recoverable magnetic popcorn chicken catalyst CuS/Fe of claim 8 3 O 4 Characterized in that in step six, the Fe is 3 O 4 The mass of (2) was 0.144g.
10. The electronic of claim 9Magnetic popcorn chicken catalyst CuS/Fe with high transfer rate and easy recovery 3 O 4 The method for preparing (1), wherein the ratio of the amount of the substance of copper chloride to the amount of the substance of thiourea in step (seven) is 1.
11. The fast electron transfer rate, easily recoverable magnetic popcorn chicken catalyst CuS/Fe of claim 10 3 O 4 The preparation method is characterized in that the operation parameters of the solvothermal reaction in the step eight are as follows: the solvothermal temperature is 180 ℃, the solvothermal time is 2 hours, and the filling degree of the reaction kettle lined with polytetrafluoroethylene is 60-70%.
12. The fast electron transfer rate, easily recoverable magnetic popcorn chicken catalyst CuS/Fe of claim 11 3 O 4 The preparation method is characterized in that the washing process in the step nine is as follows: and alternately washing with ethanol and deionized water for 3 times.
13. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 12 3 O 4 The preparation method is characterized in that the drying process in the step nine is as follows: vacuum drying at 60 deg.c for 8-10 hr.
14. The fast electron transfer rate, easily recoverable magnetic popcorn chicken catalyst CuS/Fe of claim 1 3 O 4 Characterized by using magnetic popcorn-like CuS/Fe 3 O 4 Used as a catalyst to activate persulfate to treat dye wastewater.
15. The fast electron transfer rate, easily recoverable magnetic popcorn catalyst CuS/Fe of claim 14 3 O 4 The method is characterized in that the dye wastewater is methyl orange wastewater.
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