A Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalytic material and preparation method and application thereof

Abstract

This invention provides a Ba x Sr 1‑x Co y Fe 1‑y O 3‑δ Perovskite catalytic materials, their preparation methods, and applications. The preparation method of the perovskite catalytic material of this invention includes the following steps: fully dispersing Ba, Sr, Co, and Fe sources in a solvent, followed by ball milling, drying, and grinding to obtain a precursor; calcining the precursor to obtain Ba… x Sr 1‑x Co y Fe 1‑ y O 3‑δ Perovskite catalytic materials. Compared with other chemical synthesis methods, the preparation method of this invention is simple, the conditions are easy to achieve, the cost is relatively low, and it can be mass-produced, showing good application prospects. The Ba prepared by this invention... x Sr 1‑x Co y Fe 1‑ y O 3‑δ Perovskite catalysts exhibit excellent performance in activating PMS to degrade BPA and phenol, and also demonstrate good stability.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, and particularly relates to a Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalytic materials, their preparation methods, and applications. Background Technology

[0002] In recent years, with the acceleration of industrialization, more and more organic matter has been discharged into water bodies, causing serious pollution, harming the ecological environment and human health, and becoming a major problem restricting global sustainable development. Most of these organic compounds have high chemical stability, making them difficult to separate from water bodies. Phenolic compounds are an important class of aromatic compounds, widely used as intermediates and raw materials in the industrial production of pharmaceuticals, herbicides, dyes, paints, papermaking, petrochemicals, and wood or leather preservatives. Phenol is a carcinogen; bisphenol A (BPA) has certain embryotoxic and teratogenic effects, affecting the growth and development of infants and causing damage to children's brains and sexual organs. Therefore, how to effectively remove both phenol and BPA simultaneously warrants further research.

[0003] Currently, physical, biological, or chemical methods are commonly used to remove organic pollutants from wastewater. However, physical methods essentially concentrate and transfer pollutants without achieving degradation; biological methods can only decompose readily biodegradable organic matter with the help of microorganisms, and their treatment effect on poorly biodegradable organic matter is not ideal; compared to the first two methods, chemical oxidation can effectively remove recalcitrant pollutants, but in practical applications, it suffers from drawbacks such as high energy consumption, low oxidant utilization rate, and secondary pollution. Advanced oxidation processes (AOPs) have become one of the most effective methods for treating recalcitrant organic pollutants due to their high efficiency and non-selectivity, and have received widespread attention. Among them, the generation of sulfate free radicals (SO42-) is particularly important. ·- Advanced oxidation technology, with SO42-based oxidation as its core, offers advantages over traditional water treatment technologies, including strong oxidizing power, rapid reaction rate, mild reaction conditions, wide applicability, and simple and easy-to-operate equipment. This technology primarily utilizes ultraviolet light, ultrasound, heat, or homogeneous / heterogeneous catalysts to activate persulfate and generate highly reactive SO42-. ·- ·OH, O2 ·- free radicals and 1 O2 is a non-radical catalyst, thus achieving efficient degradation of organic pollutants. However, ultraviolet light, ultrasound, and heat require higher energy, increasing their activation costs. Therefore, developing catalysts with high catalytic activity and stability is crucial.

[0004] Perovskite oxides, due to their diverse composition and structural stability, are widely used as catalytic materials in photocatalysis and electrochemical catalysis, cathode materials for solid oxide fuel cells, microwave dielectric ceramic materials, and piezoelectric ceramic materials. Recently, there has been some research on the application of perovskite oxides in activating persulfate (PMS) to degrade organic pollutants. For example, Chinese patent document CN113289628A discloses a magnetic perovskite catalyst. The preparation process includes: weighing soluble cobalt salt, soluble strontium salt, and soluble iron salt and dissolving them together in water to form a homogeneous solution; adding Na2CO3 solution dropwise to the homogeneous solution, stirring for 30 minutes after the addition is complete, and then letting it stand for 1 hour; filtering the solution, washing the filter residue until the pH of the filtrate is 7, then drying the washed filter residue at 80℃ for 12 hours, grinding the dried filter residue into powder to obtain the precursor; calcining the precursor at 725℃~1025℃ for 6 hours to obtain the product magnetic perovskite catalyst. This catalyst can activate persulfate to degrade the antibiotic florfenicol. However, the preparation method of this invention is relatively complex, the components are singular, and it does not involve the degradation of phenol and bisphenol A. Chinese patent document CN113856692A discloses a method for preparing a perovskite catalyst and activating it for treating atrazine wastewater with persulfate: through Sr doping with LaFe... 0.5 Cu 0.5 O3-type perovskite catalysts are prepared by means of the chemical formula La. x Sr 1- x Fe 0.5 Cu 0.5 O3 (0.1≤x≤0.9). The perovskite catalyst obtained by this invention activates persulfate to treat atrazine wastewater. However, the preparation method of this invention is relatively complex and only involves the degradation of a single organic pollutant. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalytic materials, their preparation methods, and applications. Compared to other chemical synthesis methods, the preparation method of this invention is simple, the conditions are easy to achieve, the cost is relatively low, and it can be mass-produced, showing good application prospects. The Ba prepared by this invention... x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalysts exhibit excellent performance in activating PMS to degrade BPA and phenol, and also demonstrate good stability.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A type of Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalytic material, wherein the perovskite catalytic material is Ba x Sr 1-x Co y Fe 1- y O 3-δ Perovskite-type oxides; where x ranges from 0.4 to 0.6, y ranges from 0.2 to 0.8, and 0 < δ < 3. The aforementioned δ represents the possible oxygen vacancies.

[0008] According to the present invention, preferably, the microstructure of the perovskite catalytic material is a micron-sized particle structure, wherein the particle size of the micron-sized particles is 1–100 μm.

[0009] The above Ba x Sr 1-x Co y Fe 1-y O 3-δ A method for preparing perovskite catalytic materials includes the following steps: fully dispersing Ba, Sr, Co, and Fe sources in a solvent, followed by ball milling, drying, and grinding to obtain a precursor; calcining the precursor to obtain Ba... x Sr 1- x Co y Fe 1-y O 3-δ Perovskite catalytic materials.

[0010] According to the present invention, preferably, the molar ratio of Ba, Sr, Co and Fe elements in the Ba source, Sr source, Co source and Fe source is 4-6:4-6:2-8:2-8; preferably, the molar ratio of Ba, Sr, Co and Fe elements is 4-5:5-6:8:2, and more preferably 5:5:8:2.

[0011] According to the present invention, preferably, the Ba source is BaCO3; the Sr source is SrCO3; the Co source is Co2O3; and the Fe source is Fe2O3.

[0012] According to the present invention, preferably, the solvent is anhydrous ethanol; the molar ratio of Ba source to solvent volume is 0.1-1 mol / L.

[0013] According to the present invention, preferably, the mass ratio of grinding balls to total material used in the ball mill is 10-20:1; the grinding balls are a mixture of grinding balls with diameters of 10 mm, 6 mm, and 4 mm; wherein the mass ratio of grinding balls with diameters of 10 mm, 6 mm, and 4 mm is 1:1:1. The total material refers to Ba source, Sr source, Co source, Fe source, and solvent.

[0014] According to the present invention, preferably, the ball milling speed is 200-400 rpm / min, and the milling stops for 5-15 minutes every 20-40 minutes. Automatic forward and reverse rotation is set, the ball milling time is 2-4 hours, and the ball milling temperature is room temperature.

[0015] According to the present invention, preferably, the drying temperature is 60-100℃ and the drying time is 6-10h.

[0016] According to the present invention, preferably, the grinding method is manual grinding, the grinding time is 20 minutes, and the grinding temperature is room temperature.

[0017] According to the present invention, preferably, the calcination temperature is 1000-1200℃, the calcination time is 3-7h, the heating rate is 2-8℃ / min, and the calcination atmosphere is air.

[0018] The above Ba x Sr 1-x Co y Fe 1-y O 3-δ The application of perovskite catalytic materials as catalysts for activating PMS to degrade BPA and / or phenol in wastewater.

[0019] According to the present invention, the preferred application method is as follows: Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalyst was added to wastewater and stirred at room temperature for 20-60 minutes. Then PMS was added and the mixture was stirred at room temperature for 40 minutes to 5 hours.

[0020] Preferred, Ba x Sr 1-x Co y Fe 1-y O 3-δ The dosage of perovskite catalyst is 0.01-10 g / L; the dosage of PMS is 1-20 mmol / L.

[0021] The technical features and beneficial effects of this invention are as follows:

[0022] 1. The preparation method of this invention utilizes traditional solid-phase synthesis techniques, using metal oxides and metal carbonates as raw materials and anhydrous ethanol as a solvent, to simply and effectively prepare micron-sized Ba. x Sr 1-x Co y Fe 1-y O 3-δ Perovskite oxide materials. Compared with other chemical synthesis methods, the preparation method of this invention is simple, easy to operate, and the conditions are easy to achieve. It is relatively low in cost, safe and environmentally friendly, and can be mass-produced, showing good application prospects and economic benefits.

[0023] 2. The Ba prepared by this invention x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalysts have a micron-sized particle structure with small pores, which increases the active surface area of ​​the catalyst and thus improves its catalytic activity. They have promising applications in water treatment where PMS is catalyzed to degrade organic pollutants.

[0024] 3. Ba prepared by this invention x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalysts are specifically designed for activating PMS to degrade BPA and phenol. They exhibit excellent performance in activating PMS for BPA and phenol degradation, demonstrating good degradation efficiency and stability. This invention, Ba... x Sr 1-x Co y Fe 1-y O 3-δ The perovskite catalytic material comprises the following metallic elements: Ba, Sr, Co, and Fe. Each of these elements is indispensable and exhibits complex interactions, working together to achieve the superior effects of this invention. This invention improves the efficiency of activated PMS in degrading BPA and phenol by adjusting the proportions of these four elements.

[0025] 4. Ba prepared by this invention x Sr 1-x Co y Fe 1-y O 3-δPerovskite catalysts were prepared by co-doping Ba and Sr at the A-site and Co and Fe at the B-site. A series of catalysts were prepared by adjusting the ratio of A-site and B-site elements, and the effects of controlling the types and ratios of A-site and B-site elements on the catalyst structure and performance were systematically investigated. The content and ratio of Ba, Sr, Co, and Fe elements significantly affected the degradation performance of PMS on BPA and phenol; higher Co content resulted in better degradation performance; and the degradation performance was optimal when the Ba:Sr ratio was 1:1. Among these, Ba... 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Perovskite catalysts exhibit the best performance in activating PMS to degrade BPA and phenol. Attached Figure Description

[0026] Figure 1 The X-ray diffraction patterns are those of the perovskite catalytic materials prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention.

[0027] Figure 2 This is a scanning electron microscope image of the perovskite catalyst material prepared in Example 1 of the present invention.

[0028] Figure 3 The graph shows a comparison of the degradation performance of BPA by PMS activated by the perovskite catalysts prepared in Examples 1-5 and Comparative Examples 1-2 of this invention.

[0029] Figure 4 The graph shows a comparison of the degradation performance of BPA using only the perovskite catalyst prepared in Example 1, using only PMS, and using the catalyst / PMS system.

[0030] Figure 5 The graph shows a comparison of the degradation performance of phenol by PMS activated by the perovskite catalysts prepared in Examples 1-5 and Comparative Examples 1-2 of this invention. Detailed Implementation

[0031] The present invention will now be described in detail. Before proceeding with the description, it should be understood that the terminology used in this specification and the appended claims should not be construed as limited to its general or dictionary meaning, but rather should be interpreted according to the meaning and concept corresponding to the technical aspects of the invention, based on the principle that the inventors are allowed to appropriately define the terms for the best interpretation. Therefore, the description presented herein is merely a preferred example for illustrative purposes and is not intended to limit the scope of the invention. It should be understood that other equivalents or modifications can be obtained from it without departing from the spirit and scope of the invention.

[0032] The following embodiments are merely examples illustrating implementations of the present invention and do not constitute any limitation on the present invention. Those skilled in the art will understand that modifications made without departing from the spirit and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, the reagents and instruments used in the following embodiments are commercially available products.

[0033] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0034] Example 1

[0035] A type of Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0036] (1) Weigh out 5 mmol BaCO3, 5 mmol SrCO3, 4 mmol Co2O3 and 1 mmol Fe2O3.

[0037] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0038] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0039] Scanning electron microscope (SEM) images of the perovskite catalyst material prepared in this embodiment are shown below. Figure 2 As shown in the figure, Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The material has a micron-sized particle structure with protrusions on the particles, which may be caused by segregation.

[0040] It also has a porous structure.

[0041] Example 2

[0042] A type of Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0043] (1) Weigh out 6 mmol BaCO3, 4 mmol SrCO3, 4 mmol Co2O3 and 1 mmol Fe2O3.

[0044] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0045] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0046] Example 3

[0047] A type of Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0048] (1) Weigh out 4 mmol BaCO3, 6 mmol SrCO3, 4 mmol Co2O3 and 1 mmol Fe2O3.

[0049] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0050] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0051] Example 4

[0052] A type of Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0053] (1) Weigh out 5 mmol BaCO3, 5 mmol SrCO3, 2.5 mmol Co2O3 and 2.5 mmol Fe2O3.

[0054] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0055] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0056] Example 5

[0057] A type of Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0058] (1) Weigh out 5 mmol BaCO3, 5 mmol SrCO3, 1 mmol Co2O3 and 4 mmol Fe2O3.

[0059] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0060] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0061] Comparative Example 1

[0062] A BaCo 0.8 Fe 0.2 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0063] (1) Weigh out 10 mmol BaCO3, 4 mmol Co2O3 and 1 mmol Fe2O3.

[0064] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0065] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0066] Comparative Example 2

[0067] A SrCo 0.8 Fe 0.2 O 3-δ Perovskite catalytic materials, wherein 0 < δ < 3, are prepared by the following method:

[0068] (1) Weigh out 10 mmol SrCO3, 4 mmol Co2O3 and 1 mmol Fe2O3.

[0069] (2) Disperse the raw materials weighed in step (1) in 15 mL of anhydrous ethanol. Weigh stainless steel balls at a ball-to-material mass ratio of 15:1, with grinding balls of diameters of 10 mm, 6 mm, and 4 mm in a mass ratio of 1:1:1. Set the ball mill speed to 300 rpm / min, with a 10-min pause every 30 min, automatic forward and reverse rotation, a ball milling time of 3 h, and a ball milling temperature of room temperature. Transfer the ball-milled mixture to a vacuum drying oven and dry it at 80℃ for 8 h. Then grind it in a mortar at room temperature for 20 min to make it homogeneous, obtaining the mixture precursor.

[0070] (3) The mixture precursor obtained in step (2) is placed in a muffle furnace and calcined in an air atmosphere. The temperature is programmed to rise from room temperature to 1100℃ at a rate of 5℃ / min, and then held at that temperature for 5h to obtain a black powder sample.

[0071] Experimental Example 1

[0072] The X-ray diffraction patterns of the perovskite catalysts prepared in Examples 1-5 and Comparative Examples 1-2 are as follows: Figure 1 As shown in the figure, the Ba prepared in Examples 1-5 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ The perovskite catalyst corresponds to the 23-1023 PDF card of the tetragonal crystal system; Comparative Example 1 prepared BaCo 0.8 Fe 0.2 O 3-δ The catalyst corresponds to the hexagonal crystal system 74-0646 PDF card; Comparative Example 2 prepared SrCo 0.8 Fe0.2 O 3-δ The catalyst corresponds to PDF card 82-2445 for the cubic crystal system. Furthermore, with increasing Sr content, the diffraction peaks gradually shift to higher angles, indicating a decrease in the lattice spacing of the material. This is likely due to the substitution of some Ba ions by Sr ions with smaller ionic radii.

[0073] Application Example 1

[0074] The specific steps for applying perovskite catalysts in the catalytic activation of PMS to degrade BPA in wastewater are as follows:

[0075] (1) Simulated wastewater sample, the target pollutant in the wastewater is BPA, and the concentration of BPA is 20 mg / L. That is, an aqueous solution of BPA;

[0076] (2) Add Ba prepared in Examples 1, 2, 3, 4, and 5 to the simulated sewage sample. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ BaCo prepared in Comparative Examples 1 and 2 0.8 Fe 0.2 O 3-δ SrCo 0.8 Fe 0.2 O 3-δ The perovskite catalyst was added at a concentration of 0.1 g / L. After mixing evenly, the mixture was stirred at room temperature for 30 min to reach adsorption equilibrium. Then, PMS (3.25 mM) was added, stirred, and reacted at room temperature for 60 min. Samples were taken every 10 min, and 1 mL of the sample solution was filtered through a 0.22 μm filter. The sample solution was then mixed with 0.5 mL of methanol to quench free radicals. The content of organic pollutants in the sample solution was detected by high performance liquid chromatography.

[0077] Figure 3Ba prepared in Examples 1, 2, 3, 4, and 5 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ BaCo prepared in Comparative Examples 1 and 2 0.8 Fe 0.2 O 3-δ SrCo 0.8 Fe 0.2 O 3-δ Comparison of the performance of perovskite catalytic materials in activating PMS to degrade BPA.

[0078] Depend on Figure 3 It can be seen that the Ba prepared in Example 1 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The perovskite catalyst activated PMS and degraded 91% of BPA within 10 min, demonstrating better catalytic activation performance than the perovskite catalysts prepared in Examples 2, 3, 4, 5 and Comparative Examples 1, 2.

[0079] Figure 4 Ba prepared in Example 1 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Comparison of the degradation performance of BPA by perovskite catalyst alone (i.e., without PMS), PMS alone, and catalyst / PMS system.

[0080] Depend on Figure 4 It can be seen that the Ba prepared in Example 1 0.5 Sr 0.5 Co 0.8 Fe 0.2O 3-δ Neither perovskite catalysts nor PMS alone had a significant effect on the degradation of BPA, while Ba... 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Activated PMS showed excellent degradation effect on BPA.

[0081] Application Example 2

[0082] The specific steps for applying perovskite catalysts in the catalytic degradation of phenol in wastewater using PMS are as follows:

[0083] (1) Simulated wastewater sample, the target pollutant in the wastewater is phenol, the concentration of phenol is 20 mg / L, that is, an aqueous solution of phenol;

[0084] (2) Add Ba prepared in Examples 1, 2, 3, 4, and 5 to the simulated sewage sample. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ BaCo prepared in Comparative Examples 1 and 2 0.8 Fe 0.2 O 3-δ SrCo 0.8 Fe 0.2 O 3-δ The perovskite catalyst was added at a concentration of 0.1 g / L. After mixing evenly, the mixture was stirred at room temperature for 30 min to reach adsorption equilibrium. Then, PMS (6.5 mM) was added, stirred, and reacted at room temperature for 60 min. Samples were taken every 10 min. 1 mL of the sample solution was filtered through a 0.22 μm filter and then mixed with 0.5 mL of methanol to quench free radicals. The content of organic pollutants in the sample solution was detected by high performance liquid chromatography.

[0085] Figure 5 Ba prepared in Examples 1, 2, 3, 4, and 5 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ Ba 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ Ba 0.4 Sr 0.6 Co 0.8 Fe 0.2 O 3-δ Ba 0.5 Sr 0.5 Co 0.5 Fe 0.5 O 3-δ Ba 0.5 Sr 0.5 Co 0.2 Fe 0.8 O 3-δ BaCo prepared in Comparative Examples 1 and 2 0.8 Fe 0.2 O 3-δ SrCo 0.8 Fe 0.2 O 3-δ Comparison of the performance of perovskite catalytic materials in activating PMS to degrade phenol.

[0086] Depend on Figure 5 It can be seen that the Ba prepared in Example 1 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ The perovskite catalyst activated PMS and degraded 83% of phenol within 10 min, and the degradation rate of phenol was close to 100% within 30 min, showing better catalytic activation performance than the perovskite catalysts prepared in Examples 2, 3, 4, 5 and Comparative Examples 1, 2.

[0087] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.

Claims

1. A Ba x Sr 1-x Co y Fe 1-y O 3-δ perovskite catalytic material for use in a process for the production of hydrogen from a hydrocarbon feedstock, characterised in that, It can be used as a catalyst to activate PMS for the degradation of BPA in wastewater; The Ba x Sr 1-x Co y Fe 1-y O 3-δ The perovskite catalyst is Ba x Sr 1-x Co y Fe 1-y O 3-δ Perovskite oxide; where x is 0.5, y is 0.8, and 0 < δ < 3; The perovskite catalytic material has a micron-sized particle structure with a particle size of 1–100 μm. The Ba x Sr 1-x Co y Fe 1-y O 3-δ A method for preparing perovskite catalytic materials includes the following steps: fully dispersing Ba, Sr, Co, and Fe sources in a solvent, followed by ball milling, drying, and grinding to obtain a precursor; calcining the precursor to obtain Ba... x Sr 1-x Co y Fe 1- y O 3-δ Perovskite catalytic materials; Among the Ba, Sr, Co, and Fe sources, the molar ratio of Ba, Sr, Co, and Fe is 5:5:8:2; the Ba source is BaCO3; the Sr source is SrCO3; the Co source is Co2O3; and the Fe source is Fe2O3. The calcination temperature is 1000-1200 ℃, the calcination time is 3-7 h, the heating rate is 2-8 ℃ / min, and the calcination atmosphere is air. The solvent is anhydrous ethanol; the molar ratio of Ba source to solvent volume is 0.1-1 mol / L; the mass ratio of grinding balls to total material used in ball milling is 10-20:1; the grinding balls are a mixture of grinding balls with diameters of 10 mm, 6 mm, and 4 mm; wherein the mass ratio of grinding balls with diameters of 10 mm, 6 mm, and 4 mm is 1:1:1; the ball milling speed is 200-400 rpm / min, with a 5-15 min pause every 20-40 min, automatic forward and reverse rotation is set, the ball milling time is 2-4 h, and the ball milling temperature is room temperature; the drying temperature is 60-100 ℃, and the drying time is 6-10 h; the grinding method is manual grinding, the grinding time is 20 min, and the grinding temperature is room temperature.

2. The Ba according to claim 1 x Sr 1-x Co y Fe 1-y O 3-δ The application of perovskite catalytic materials is as follows: Ba... x Sr 1-x Co y Fe 1-y O 3-δ Perovskite catalyst was added to wastewater and stirred at room temperature for 20-60 min. PMS was then added, and the reaction was continued at room temperature with stirring for 40 min-5 h. Ba x Sr 1-x Co y Fe 1-y O 3-δ The dosage of perovskite catalyst is 0.01-10 g / L; the dosage of PMS is 1-20 mmol / L.

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