CN110102314B - S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, catalytic system, preparation method and application thereof - Google Patents
S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, catalytic system, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to S-Cu 1‑X Co X Fe 2 O 4 Fenton-like catalyst, catalytic system, preparation method and application thereof. The preparation method comprises the following steps: s1: mixing and dissolving a copper source, a cobalt source and a ferric iron source, adding a solvent, and carrying out hydrothermal reaction to obtain Cu 1‑ X Co X Fe 2 O 4 Powder; s2: mixing Cu 1‑X Co X Fe 2 O 4 Adding the powder into a sulfuric acid solution, and stirring for reaction to obtain powder; s3: calcining the powder to obtain the S-Cu 1‑X Co X Fe 2 O 4 A fenton-like catalyst. The preparation method provided by the invention has the advantages of simple process, wide material source, low cost and environmental friendliness; preparation to obtain S-Cu 1‑X Co X Fe 2 O 4 The Fenton-like catalyst has high catalytic activity, wide application range, high reaction rate and easy recovery, and is easy to react with HCO 3 ‑ /H 2 O 2 And by combining the two methods, various refractory organic substances can be quickly removed, particularly refractory organic substances such as antipyrine, acid orange II and the like.
Description
Technical Field
The invention belongs to the field of water treatment catalytic materials, and particularly relates to S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, catalytic system, preparation method and application thereof.
Background
Along with the increasing pollution problem, the water environment pollutants have rich sources and complex components. In particular, the environmental pollution and potential impact problems of some new trace pollutants, such as drugs (e.g., anti-inflammatory drugs, antibiotics, sedatives, etc.) and personal care products (PPCPs, e.g., cosmetics, toothpaste, hair care products, etc.), endocrine disruptors (EDCs, e.g., bisphenol a, polychlorinated biphenyl, etc.), perfluoro-based compounds (PFCs, e.g., perfluorotetradecanoic acid, perfluorooctanoic acid, perfluorononanoic acid, etc.), etc., have been the focus of attention of various national and public people. People face new challenges and higher requirements for solving the pollution problem. The Fenton-like catalyst technology is one of advanced oxidation technologies, overcomes the defects of iron mud generation and strict pH condition in homogeneous Fenton, and can be recycled to avoid secondary pollution. And thus has received wide attention as a green promising technology. Ferrite with spinel structure is a common Fenton-like catalyst due to wide material sources, but the ferrite itself needs to consume a large amount of H 2 O 2 Etc. by their own characteristics.
Therefore, a catalyst which has high catalytic activity and can rapidly degrade hardly degradable organic substances and H has been developed 2 O 2 The novel Fenton-like catalyst with low consumption has important research significanceAnd (5) defining.
Disclosure of Invention
The invention aims to overcome the defects that the Fenton-like catalyst in the prior art has low catalytic activity, slow degradation of refractory organic substances and large consumption of H 2 O 2 To provide an S-Cu 1-X Co X Fe 2 O 4 A preparation method of the Fenton-like catalyst. The preparation method provided by the invention has the advantages of simple process, wide material source, low cost and environmental friendliness; preparation of the obtained S-Cu 1- X Co X Fe 2 O 4 The Fenton-like catalyst has high catalytic activity, wide application range, high reaction rate and easy recovery, and is easy to react with HCO 3 - /H 2 O 2 Can quickly remove various refractory organic substances, in particular refractory organic substances such as antipyrine, acid orange II and the like, H 2 O 2 The consumption is small.
Another object of the present invention is to provide an S-Cu 1-X Co X Fe 2 O 4 A fenton-like catalyst.
Another object of the present invention is to provide the above S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst is applied to the field of sewage treatment.
It is another object of the present invention to provide a catalyst system.
In order to achieve the purpose, the invention adopts the following technical scheme:
S-Cu 1-X Co X Fe 2 O 4 The preparation method of the Fenton-like catalyst comprises the following steps:
s1: mixing and dissolving a copper source, a cobalt source and a ferric iron source, adding a surfactant, stirring, adjusting the pH to 8.0-9.0, stirring, carrying out hydrothermal reaction at 180-200 ℃ for 24 hours, washing, carrying out magnetic separation, drying, and grinding to obtain Cu 1-X Co X Fe 2 O 4 Powder;
s2: mixing Cu 1-X Co X Fe 2 O 4 Adding the powder into a sulfuric acid solution, stirring for reaction, filtering, washing, drying and grinding into powder;
s3: calcining the powder at 500-600 ℃ for 2-4 h to obtain the S-Cu 1-X Co X Fe 2 O 4 A fenton-like catalyst;
wherein X is more than or equal to 0.25 and less than or equal to 0.75.
The invention utilizes a hydrothermal method to prepare Cu 1-X Co X Fe 2 O 4 Powder, then modifying Cu with S 1-X Co X Fe 2 O 4 The performance of the catalyst is improved, the activity of the catalyst is improved, the preparation process is simple, the material source is wide, the cost is low, and the environment is friendly; preparation to obtain S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst has high catalytic activity, wide application range, high reaction rate and easy recovery, and is easy to react with HCO 3 - /H 2 O 2 And by combining the two methods, various refractory organic substances can be quickly removed, particularly refractory organic substances such as antipyrine, acid orange II and the like.
Copper sources, cobalt sources, ferric sources, as are conventional in the art, may be used in the present invention.
Preferably, the copper source in S1 is one or more of copper nitrate, copper sulfate or copper chloride.
Preferably, the cobalt source in S1 is one or more of cobalt nitrate, cobalt sulfate or cobalt chloride.
Preferably, the ferric iron source in S1 is one or more of ferric nitrate or ferric chloride.
Preferably, the solvent in S1 is one or more of ethylene glycol or polyethylene glycol.
Preferably, in S1, X is 0.75.
Preferably, the pH is adjusted to 8 in S1.
Preferably, the pH is adjusted in S1 with ammonia.
Preferably, the temperature of the hydrothermal reaction is 180 ℃ and the time is 24 h.
Preferably, the washing process is washing by deionized water and absolute ethyl alcohol in sequence.
Preferably, the concentration of the sulfuric acid solution in S2 is 0.5-1.0 mol/L.
Preferably, Cu in S2 1-X Co X Fe 2 O 4 The mass mol ratio of the powder to the sulfuric acid is 80-160: 1 g/mol.
Preferably, the calcination in S3 is carried out at 500 ℃ for 2 h.
S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst is prepared by the preparation method.
Preferably, the S-Cu 1-X Co X Fe 2 O 4 The particle size of the Fenton-like catalyst is 30-40 nm.
Preferably, the S-Cu 1-X Co X Fe 2 O 4 The mass fraction of S in the Fenton-like catalyst is 2.0-4.0%.
The above-mentioned S-Cu 1-X Co X Fe 2 O 4 The application of the Fenton-like catalyst in the field of sewage treatment is also within the protection scope of the invention.
Preferably, the S-Cu 1-X Co X Fe 2 O 4 Use of a fenton-like catalyst in the treatment of wastewater containing pharmaceuticals or personal care products.
Preferably, the medicine is one or more of anti-inflammatory drugs, antibiotics or sedatives; the personal care product is one or more of cosmetics, toothpaste or hair care agents; the endocrine disrupter is one or more of bisphenol A or polychlorinated biphenyl; the perfluoro compound is one or more of perfluoro tetradecanoic acid, perfluoro caprylic acid or perfluoro pelargonic acid.
More preferably, the S-Cu 1-X Co X Fe 2 O 4 Application of Fenton-like catalyst in treatment of PPCPs, endocrine disruptors or dye wastewater sewage.
The invention also claims a catalyst system comprising the S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst and HCO 3 - /H 2 O 2 。
Bicarbonate radical (HCO) 3 - ) Is a common anion and widely exists in natural water bodies.Bicarbonate activated hydrogen peroxide (HCO) 3 - /H 2 O 2 ) The Fenton-like system combined with metal ions or catalysts and formed as an emerging wastewater treatment technology has been proved to be capable of degrading various dyes and other wastewater.
The invention uses S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst and HCO 3 - /H 2 O 2 The catalyst system can degrade various refractory organic substances, especially refractory organic substances such as antipyrine, acid orange II and the like.
S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, HCO 3 - And H 2 O 2 The proportion relation of the three can refer to the existing conditions.
Preferably, the catalyst system comprises S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, HCO 3 - And H 2 O 2 The molar ratio of (A) to (B) is 3-10: 1: 6.8-20.4.
More preferably, the catalyst system comprises S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, HCO 3 - And H 2 O 2 In a molar ratio of 3:1: 17.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention has the advantages of simple process, wide material source, low cost and no pollution to the environment; preparation of the obtained S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst not only maintains the catalytic performance of the unit metal catalyst, but also has the synergistic interaction effect among metals, has high catalytic activity, wide application range, mild reaction conditions, simplicity and feasibility, and can quickly degrade refractory organic substances such as medicaments, PPCPs and the like.
Drawings
FIG. 1 shows S-Cu provided in example 1 of the present invention 0.25 Co 0.75 Fe 2 O 4 A scanning electron micrograph of the Fenton-like catalyst;
FIG. 2S-Cu provided for inventive example 1 0.25 Co 0.75 Fe 2 O 4 XPS spectra of fenton-like catalysts;
FIG. 3 is a S-Cu diagram provided in example 1 of the present invention 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst and Cu 1-X Co X Fe 2 O 4 The effect of the fenton-like catalyst on the removal of antipyrine;
FIG. 4 shows S-Cu provided in example 1 of the present invention 0.25 Co 0.75 Fe 2 O 4 The Fenton-like catalyst has the effect of removing antipyrine under different catalyst dosages;
FIG. 5 shows S-Cu provided in example 1 of the present invention 0.25 Co 0.75 Fe 2 O 4 The Fenton-like catalyst has the effect of removing acid orange II under different catalyst dosages;
FIG. 6 shows S-Cu provided in example 1 of the present invention 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst and CuFeO 2 And CoFeO 2 Removal effect on antipyrine.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides an S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalysts, including in particular S-Cu 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst, S-Cu 0.5 Co 0.5 Fe 2 O 4 Fenton-like catalyst, S-Cu 0.75 Co 0.25 Fe 2 O 4 A fenton-like catalyst.
Prepared by the following method.
(1) 8.08g of iron nitrate (Fe (NO) were weighed 3 ) 3 ·9H 2 O), 2.18g of cobalt nitrate (Co (NO) 3 ) 3 ·6H 2 O) and 0.60g of copper nitrate (S-Cu (NO) 3 ) 3 ·6H 2 O) putting the mixture into a beaker, adding 30mL of deionized water, stirring the mixture to be completely dissolved, adding 50mL of glycol surfactant, magnetically stirring the mixture for 30min, dropwise adding ammonia water until the pH value of the solution is 8, continuously magnetically stirring the mixture for 1h, transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate, reacting the mixture for 24h at 180 ℃, naturally cooling the mixture to room temperature, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, magnetically separating the precipitates, drying the precipitates in an oven at 60 ℃ for 12h in vacuum, and finally grinding the precipitates to obtain Cu 0.25 Co 0.75 Fe 2 O 4 And (3) powder.
Adjusting cobalt nitrate (Co (NO) in step (1) 3 ) 2 ·6H 2 O in an amount of 1.45g and copper nitrate (Cu (NO) 3 ) 2 ·6H 2 O) in an amount of 1.21g, Cu was prepared 0.5 Co 0.5 Fe 2 O 4 And (3) powder.
Adjusting cobalt nitrate (Co (NO) in step (1) 3 ) 2 ·6H 2 O in an amount of 0.73g and copper nitrate (Cu (NO) 3 ) 2 ·6H 2 O) in an amount of 1.81g, Cu was prepared 0.75 Co 0.25 Fe 2 O 4 And (3) powder.
(2) 4g of Cu 0.25 Co 0.75 Fe 2 O 4 Powder, 4g Cu 0.5 Co 0.5 Fe 2 O 4 Powder, 4g Cu 0.75 Co 0.25 Fe 2 O 4 The powder is respectively put into a hopper with the concentration of 0.5mol/L H 2 SO 4 In a 50mL beaker of the solution, the mixture was stirred for 1 hour with strong magnetic force at 40 ℃ and then filtered, and the obtained precipitate was washed with deionized water and absolute ethanol, vacuum-dried at 60 ℃ for 6 hours, and ground into powder.
(3) Then the dried powder is placed in a muffle furnace to be calcined for 2 hours at the temperature of 500 ℃ to respectively obtain S-Cu 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst, S-Cu 0.5 Co 0.5 Fe 2 O 4 Fenton-like catalyst, S-Cu 0.75 Co 0.25 Fe 2 O 4 A fenton-like catalyst.
As shown in FIG. 1, is S-Cu 0.25 Co 0.75 Fe 2 O 4 The Fenton-like catalyst has a particle size of about 40nm in a scanning electron microscope image; S-Cu 0.5 Co 0.5 Fe 2 O 4 Fenton-like catalyst, S-Cu 0.75 Co 0.25 Fe 2 O 4 The particle size of the fenton-like catalyst is also about 40 nm.
FIG. 2 shows S-Cu 0.25 Co 0.75 Fe 2 O 4 From the XPS spectrum of the Fenton-like catalyst, the XPS spectrum peak of Fe2p shows Fe at 710.90eV and 724.00eV 3+ Are present. Co2p showed Co presence at 780.40eV, 783.00eV, and 796.30eV 2 + Are present. The XPS spectrum peak of Cu2p shows that Cu2p3/2 corresponds to 934.00eV, and Cu is shown in 2+ Are present. The wide peak of S2p is around 168.40eV, mainly S 6+ Are present. The results show that, after S modification, Fe 3+ 、Co 2+ 、Cu 2+ And S 6+ The catalyst is present on the surface of the catalyst and contains 2.0 to 4.0% of S element.
Example 2
This example provides an S-Cu 0.25 Co 0.75 Fe 2 O 4 The Fenton-like catalyst is prepared by the following method.
(1) 8.08g of iron nitrate (Fe (NO) was weighed 3 ) 3 ·9H 2 O), 2.11g of cobalt sulfate (CoSO) 4 ·7H 2 O) and 0.62g copper sulfate (CuSO) 4 ·5H 2 O) putting the mixture into a beaker, adding 30mL of deionized water, stirring the mixture to be completely dissolved, adding 50mL of polyethylene glycol surfactant, magnetically stirring the mixture for 30min, dropwise adding ammonia water until the pH value of the solution is 10, continuously magnetically stirring the solution for 1h, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate, reacting the solution for 24h at 180 ℃, naturally cooling the solution to room temperature, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, magnetically separating the precipitates, and putting the precipitates into a 60 ℃ oven to be subjected to vacuum separation Drying for 12h, and finally grinding to obtain Cu 0.25 Co 0.75 Fe 2 O 4 A catalyst powder. The particle size was about 16 nm.
(2) 2.0g of Cu 0.25 Co 0.75 Fe 2 O 4 Powder input 0.5mol/L H 2 SO 4 In a 50mL beaker of the solution, the mixture was stirred for 1 hour with strong magnetic force at 40 ℃ and then filtered, and the obtained precipitate was washed with deionized water and absolute ethanol, vacuum-dried at 60 ℃ for 6 hours, and ground into powder.
(3) Then the dried powder is placed in a muffle furnace to be calcined for 4 hours at the temperature of 500 ℃ to obtain S-Cu 0.25 Co 0.75 Fe 2 O 4 A fenton-like catalyst. The particle size is about 40 nm.
Example 3
This example provides an S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst is prepared by the following method.
(1) 5.41g of ferric chloride (FeCl) was weighed 3 ·6H 2 O), 1.78g of cobalt chloride (CoCl) 2 ·6H 2 O) and 0.43g of copper chloride (CuCl) 2 ·6H 2 O) is put into a beaker, 30mL of deionized water is added and stirred to be completely dissolved, 50mL of glycol solvent is added, ammonia water is added dropwise after magnetic stirring for 30min until the pH value of the solution is 9, the magnetic stirring is continued for 1h, the solution is transferred into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate to react for 20h at 200 ℃, after the solution is naturally cooled to the room temperature, precipitates are washed for 3 times by the deionized water and absolute ethyl alcohol respectively, and are dried for 12h in a 60 ℃ oven after magnetic separation, and finally Cu is obtained by grinding 0.25 Co 0.75 Fe 2 O 4 A catalyst powder.
(2) 3.0g of Cu 0.25 Co 0.75 Fe 2 O 4 Powder input 0.5mol/L H 2 SO 4 In a 50mL beaker of the solution, the mixture was stirred for 1 hour with strong magnetic force at 40 ℃ and then filtered, and the obtained precipitate was washed with deionized water and absolute ethanol, vacuum-dried at 60 ℃ for 6 hours, and ground into powder.
(3) Then the dried powder is placed in a muffle furnace to be calcined for 4 hours at the temperature of 500 ℃ to obtain S-Cu 0.25 Co 0.75 Fe 2 O 4 A fenton-like catalyst. The particle size is about 40 nm.
S-Cu prepared as in example 1 1-X Co X Fe 2 O 4 Fenton-like catalyst, antipyrine and acid orange II which are refractory organic substances are taken as examples to measure the performance of the Fenton-like catalyst for catalyzing and degrading the refractory organic substances.
(1) Example 1 provides S-Cu 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst and Cu 1-X Co X Fe 2 O 4 Effect of Fenton-like catalyst on removal of antipyrine
0.5g/L of S-Cu provided in example 1 was added to 50mL of antipyrine solution at a concentration of 50mg/L and to the wastewater at pH 8.35 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst and 50mmol H 2 O 2 (A) Reacting at room temperature for 40min, and adding only 0.5g/L S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst (B) with addition of only 50mmol H 2 O 2 (C)、0.5g/L Cu 0.25 Co 0.75 Fe 2 O 4 And 50mmol H 2 O 2 (D)、 0.5g/LCu 0.5 Co 0.5 Fe 2 O 4 And 50mmol H 2 O 2 (E)、0.5g/LCu 0.75 Co 0.25 Fe 2 O 4 And 50mmol H 2 O 2 (F) The effect of degradation was compared. The degradation rate is shown in FIG. 3. As can be seen from FIG. 3, S-Cu 1-X Co X Fe 2 O 4 The Fenton-like catalyst (B) basically has no adsorption effect on antipyrine; h 2 O 2 (C) The oxidation effect is less than 10 percent. Multi-metal catalysts can catalyze H 2 O 2 The antipyrine is rapidly degraded. Wherein, Cu 0.25 Co 0.75 Fe 2 O 4 (94.38%) higher than Cu 0.5 Co 0.5 Fe 2 O 4 (89.17%) and Cu 0.75 Co 0.25 Fe 2 O 4 (69.87%). And S-Cu after modification of the catalyst by sulfur (S) modification 0.25 Co 0.75 Fe 2 O 4 The degradation rate reachesTo 97.80%. Therefore, the S modification further improves the catalytic performance of the catalyst.
(2) Example 1 provides S-Cu 0.25 Co 0.75 Fe 2 O 4 Effect of Fenton-like catalyst on removing antipyrine under different catalyst dosage
0, 0.1, 0.3, 0.5, 0.7 and 1.0g/L of S-Cu provided in example 1 were added to 50mL of an antipyrine solution having a concentration of 50mg/L and a pH of 8.35, respectively 1-X Co X Fe 2 O 4 Fenton-like catalyst and 50mmol H 2 O 2 The reaction was carried out at room temperature for 40min, and the degradation rate was as shown in FIG. 4. As can be seen from FIG. 4, when the amount of catalyst added was 0g/L, i.e., in the absence of catalyst, HCO was present 3 - /H 2 O 2 The removal rate of the system to ANT is less than 10%. With the continuous increase of the adding amount of the catalyst, the removal rate of antipyrine is continuously increased. When the adding amount of the catalyst is 0.3g/L, ANT is basically and completely removed within 40 min; with the further increase in the amount of catalyst, the ANT removal rate was substantially the same, or even decreased. Large catalytic consumption of H by excess catalyst 2 O 2 At the same time, the reaction between ANT and produced-OH radicals may be hindered, thereby being disadvantageous to the removal of ANT. Therefore, the optimum amount of catalyst to be added is 0.3 g/L.
(3) Example 1 provides S-Cu 0.25 Co 0.75 Fe 2 O 4 Removal effect of Fenton-like catalyst on acid orange II
To 50mL of acid orange II solution with a concentration of 100mg/L was added 0.3g/L of S-Cu provided in example 1 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst, 0.1g/L NaHCO 3 And 30mmol/L H 2 O 2 When the reaction is carried out for 10min at room temperature, the decolorization rate of the catalyst provided in example 1 can reach 100%, as shown in fig. 5.
(4) Example 1 provides S-Cu 0.25 Co 0.75 Fe 2 O 4 Removal effect of Fenton-like catalyst on acid orange II under different catalyst dosage
In 50mL of acid orange II solution with the concentration of 100mg/L0, 0.1, 0.3, 0.5 and 1.0 g/L of S-Cu as provided in example 1 were added 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst, 0.1g/L NaHCO 3 And 30mmol/L H 2 O 2 The reaction was carried out at room temperature for 10 min.
As shown in fig. 5. Similar to the degradation of antipyrine, the decolorization rate of acid orange II is continuously improved along with the continuous increase of the adding amount of the catalyst. When the adding amount of the catalyst is 0.3g/L, the decolorization rate of the acid orange II can reach 100 percent after the reaction is carried out for 10 min.
(5) Example 1 provides S-Cu 0.25 Co 0.75 Fe 2 O 4 Fenton-like catalyst and CuFeO 2 And CoFeO 2 The effect of antipyrine removal is shown in FIG. 6, the treatment procedure is the same as that in (4), and when the addition amount of each catalyst is 0.3g/L, the reaction is carried out for 10 min.
As can be seen from the figure, S-Cu 0.25 Co 0.75 Fe 2 O 4 The removal rate of the fenton-like catalyst to antipyrine in 40min is 97.80 percent, which is respectively higher than that of CuFeO 2 Catalyst (34.85%) and CoFeO 2 Catalyst (31.02%). Illustrating S-modified S-Cu 0.25 Co 0.75 Fe 2 O 4 The Fenton-like catalyst shows better catalytic performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. S-Cu 1-X Co X Fe 2 O 4 The preparation method of the Fenton-like catalyst is characterized by comprising the following steps of:
s1: mixing and dissolving a copper source, a cobalt source and a ferric iron source, adding the substance A, stirring, adjusting the pH to 8.0-9.0, stirring, carrying out hydrothermal reaction at 180-200 ℃ for 24 hours, washing, carrying out magnetic separation, drying, and grinding to obtain Cu 1-X Co X Fe 2 O 4 Powder;
s2: mixing Cu 1-X Co X Fe 2 O 4 Adding the powder into a sulfuric acid solution, stirring for reaction, filtering, washing, drying and grinding into powder;
s3: calcining the powder at 500-600 ℃ for 2-4 h to obtain the S-Cu 1-X Co X Fe 2 O 4 A fenton-like catalyst;
wherein X is more than or equal to 0.25 and less than or equal to 0.75;
the substance A is one or more of ethylene glycol or polyethylene glycol.
2. The preparation method of claim 1, wherein the copper source in S1 is one or more of copper nitrate, copper sulfate or copper chloride; the cobalt source is one or more of cobalt nitrate, cobalt sulfate or cobalt chloride; the ferric iron source is one or more of ferric nitrate or ferric chloride.
3. The method according to claim 1, wherein X =0.75 in S1.
4. The method according to claim 1, wherein the sulfuric acid solution in S2 has a concentration of 0.5 to 1.0 mol/L.
5. The method according to claim 1, wherein Cu in S2 is Cu 1-X Co X Fe 2 O 4 The mass mol ratio of the powder to the sulfuric acid is 80-160: 1 g/mol.
6. S-Cu 1-X Co X Fe 2 O 4 A Fenton-like catalyst, which is produced by the production method according to any one of claims 1 to 5.
7. S-Cu according to claim 6 1-X Co X Fe 2 O 4 The Fenton-like catalyst is characterized in that S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalysisThe mass fraction of S in the agent is 2.0-4.0%.
8. S-Cu as recited in any one of claims 6 to 7 1-X Co X Fe 2 O 4 Use of a fenton-like catalyst in the treatment of wastewater containing drugs, personal care products, endocrine disruptors or perfluorinated compounds.
9. A catalyst system comprising S-Cu as claimed in any one of claims 6 to 7 1-X Co X Fe 2 O 4 Fenton-like catalyst and HCO 3 - /H 2 O 2 。
10. The catalyst system of claim 9, wherein the catalyst system comprises S-Cu 1-X Co X Fe 2 O 4 Fenton-like catalyst, HCO 3 - And H 2 O 2 The molar ratio of (A) to (B) is 3-10: 1: 6.8-20.4.
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