CN117983203A

CN117983203A - An activated persulfate catalyst and its preparation method and application

Info

Publication number: CN117983203A
Application number: CN202410243719.1A
Authority: CN
Inventors: 夏德华; 张如梦; 唐倬云; 梅吉; 麻丁仁
Original assignee: Sun Yat Sen University
Current assignee: Sun Yat Sen University
Priority date: 2024-03-04
Filing date: 2024-03-04
Publication date: 2024-05-07

Abstract

The invention discloses an activated persulfate catalyst and a preparation method and application thereof, and relates to the technical field of catalysts. The catalyst is a bismuth carbon-embedded catalyst with a chain A structure, and the preparation method comprises the following steps: s1, synthesizing Bi-MOFs by taking bismuth salt and an acyl benzene ligand as reaction substrates through hydrothermal reaction; s2, calcining the Bi-MOFs at 500-700 ℃ in an inert gas atmosphere to obtain the bismuth carbon-embedded catalyst. The bismuth carbon-embedded catalyst activates persulfate through a non-free radical direct electron transfer path, has higher activity and selectivity, and can be used for sterilizing and disinfecting specific structures and metabolic processes of target microorganisms more effectively, so that the treatment efficiency is improved; and by-product generation can be reduced, and the risks of the environment and the human body are effectively reduced.

Description

Activated persulfate catalyst and preparation method and application thereof

Technical Field

The invention relates to the technical field of catalysts, in particular to an activated persulfate catalyst, and a preparation method and application thereof.

Background

Along with the acceleration of modern life rhythm and the improvement of health consciousness of people, water treatment disinfection technology gradually becomes an important research field. However, the conventional water treatment disinfection technology often has some defects, which affect the effect and reliability in practical application. First, conventional sterilization techniques often require long processing times and complex procedures. For example, chlorine disinfection techniques require the addition of chlorine solutions to water and reaction for a certain period of time, which results in long disinfection times, complex processes and the easy occurrence of byproducts. Second, some sanitizers produce toxic substances during the disinfection process, creating potential risks to the environment and human health. For example, the use of a large amount of disinfectants containing halomethane and other substances can result in the addition of halomethane and other carcinogenic substances, further exacerbating the difficulty and risk of water treatment. Finally, conventional water treatment disinfection techniques often suffer from reliability and stability problems. For example, ultraviolet disinfection techniques are poorly adapted to various water qualities and are susceptible to color and turbidity, so that their disinfection effects are greatly limited. Therefore, in order to solve the drawbacks of the conventional water treatment disinfection technology, a new, more effective, safe, reliable and environment-friendly technology needs to be developed. The characteristics and advantages of various technologies need to be deeply explored and applied to practical application scenes so as to improve the efficiency, reliability and safety of the water treatment disinfection technology and ensure the safety of the life and health of people.

The persulfate advanced oxidation technology is an emerging water treatment disinfection technology, and has many advantages which are not available in the traditional technology. The persulfate can be stably stored under normal environmental conditions, is not easy to decompose, volatilize or be influenced by other substances, so that the persulfate has more convenience in practical application. This advantage has led to the widespread use of persulfate advanced oxidation technology in modern water treatment projects.

In the patent CN113600173A, the application of bismuth catalyst in the sterilization and disinfection of activated persulfate is proposed, in the reaction system, the persulfate is contacted with the bismuth catalyst, and the persulfate is activated to generate hydroxyl radical (OH) and sulfate radicalThe superoxide radical (O ₂ ^-), singlet oxygen (¹O₂) and other radical species attack the target strain, so that the cell wall of the target strain is broken, DNA leaks and dissolves out, and the target strain finally dies. However, on one hand, the sterilizing and disinfecting efficiency of the bismuth catalyst activated persulfate is lower, the activated persulfate is used for sterilizing the escherichia coli with the concentration of 7log ₁₀ cfu/mL for 30min, the sterilization number is only 0.9-5.87log ₁₀ cfu/mL, and the persulfate is required to be further activated under the irradiation condition of visible light (lambda is more than or equal to 420 nm), so that the sterilizing efficiency is improved, and the energy waste can be caused by the light addition assistance; on the other hand, the reaction system realizes persulfate activation by generating a free radical path, has lower activation selectivity of the free radical path, can generate more byproducts, means that a large amount of toxic and harmful substances are easily generated in the disinfection process, and other beneficial substances in the water body are influenced at the same time, so that the risk to the environment and the human body is high.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings of low sterilization and disinfection efficiency and low selectivity of the conventional bismuth catalyst for activating a persulfate system through a free radical path, and provides an activated persulfate catalyst which has a chain A structure, can activate persulfate through a non-free radical direct electron transfer path and has higher catalytic activity and selectivity.

It is another object of the present invention to provide a process for preparing the above-described activated persulfate catalyst.

Another object of the invention is to provide the use of an activated persulfate catalyst for the sterilization and disinfection of activated persulfate. The activated persulfate catalyst activates persulfate through a non-free radical direct electron transfer path, has higher catalytic activity and selectivity, and improves the disinfection efficiency of the activated persulfate.

The above object of the present invention is achieved by the following technical scheme:

The invention provides an activated persulfate catalyst, which is a bismuth carbon-embedded catalyst with a chain A structure, and a preparation method of the activated persulfate catalyst comprises the following steps:

S1, synthesizing Bi-MOFs by taking bismuth salt and an acyl benzene ligand as reaction substrates through hydrothermal reaction;

S2, calcining the Bi-MOFs at 500-700 ℃ in an inert gas atmosphere to obtain the activated persulfate catalyst.

The bismuth-intercalated carbon catalyst with chain A structure is prepared by preparing Bi-MOFs with bismuth salt and acyl benzene ligands, calcining the Bi-MOFs in situ, controlling the calcining temperature, connecting Bi microspheres in a carbon layer, and combining the Bi microspheres with the interface of the carbon layer to form Bi-C bonds.

On one hand, the bismuth carbon-embedded catalyst can activate persulfate through a non-free radical direct electron transfer path, so that the disinfection efficiency of the activated persulfate is improved; the principle is as follows: based on the interface combination of Bi microspheres and a carbon layer to form Bi-C bonds, electrons between the Bi microspheres and the carbon layer are rearranged, so that the Bi microspheres and the carbon layer have Electronic Metal carrier interaction (Electronic Metal-Support Interaction, EMSI), electrons are transferred from Bi to the carbon layer through a Bi-C bond group EMSI coordination structure, the electron rearrangement of Bi-C is favorable for forming an intermediate complex (cat-PS) with Persulfate (PS), so that higher activation function is caused, the dominant Electron Transfer Path (ETP) process of the system is enhanced, and the damage of cells is aggravated. In addition, bismuth carbon intercalation itself can cause bacteria to be damaged by extracellular electron transfer, and small amounts of free radicals generated in the system can also cause damage to bacteria. On the other hand, the bismuth carbon-embedded catalyst has stronger stability, is not easy to leak metal ions, and has good cycle performance and safety.

In the preparation method of the bismuth carbon-embedded catalyst, the calcination temperature (500-700 ℃) needs to be precisely controlled so as to ensure that good interface bonding is formed between the Bi microspheres and the carbon layer, thereby effectively forming Bi-C bonds and improving the stability and catalytic performance of the material. If the calcining temperature is too high, the sintering or structural change of the carbon layer can be caused, so that the interface combination of the Bi microspheres and the carbon layer is incomplete or is decomposed, the formation of Bi-C bonds is affected, and the stability and the catalytic performance of the material are weakened. In contrast, if the calcination temperature is too low, the interfacial bonding of the Bi microspheres and the carbon layer may not be completely achieved, thereby affecting the formation of Bi-C bonds, reducing the stability and catalytic performance of the material.

In some of these embodiments, the calcination temperature is 550-650 ℃ in step S2 of the preparation method. The interface bonding degree between the Bi microspheres and the carbon layer is good. Preferably, the calcination temperature is 600+ -10deg.C, which has more remarkable catalytic performance.

In some embodiments, in step S2 of the preparation method, the calcination time is 1.5-3h, and the temperature rising rate is 3-7 ℃/min. The invention controls the temperature rising rate, which is beneficial to improving the stability of the catalyst; the too high heating rate can cause large local temperature gradient, cause uneven carbonization, influence the connectivity between Bi and carbon layers, and influence the morphology and the dimensional stability of Bi microspheres; if the temperature rising rate is too low, the carbonization reaction is slowly carried out, partial areas are possibly insufficiently carbonized, and the formation and perfection of Bi microspheres are insufficiently promoted, so that the formation of Bi-C bonds is influenced, and finally the morphology and the catalytic performance of the Bi@CC material are influenced. Preferably, the heating rate is 4-6 ℃/min, and the Bi@CC material has good morphology and catalytic performance.

In some of these embodiments, in step S1 of the preparation method thereof, the molar ratio of bismuth salt to acylbenzene ligand is 1: (1.5-2.5).

In some embodiments, the acylbenzene ligand is at least one of trimesic acid, terephthalic acid, and a phthalimide. Preferably, when the acyl benzene ligand is trimesic acid (H ₃ BTC), the bismuth carbon-embedded catalyst has higher catalytic performance.

In some embodiments, the bismuth salt is at least one of bismuth nitrate pentahydrate, bismuth chloride, bismuth nitrate.

In some embodiments, in step S1 of the preparation method, the reaction temperature of the hydrothermal reaction is 110-130 ℃ and the reaction time is 4-6h.

The invention provides a preparation method of an activated persulfate catalyst, which comprises the following steps:

S2, calcining the Bi-MOFs at 500-700 ℃ in an inert gas atmosphere to obtain the bismuth carbon-embedded catalyst.

The invention provides an application of an activated persulfate catalyst in sterilization and disinfection of activated persulfate.

The bismuth carbon-embedded catalyst is in a chain methyl structure, and can activate persulfate through a non-free radical direct electron transfer path, so that compared with the conventional persulfate sterilization and disinfection system activated through a free radical path, the bismuth carbon-embedded catalyst disclosed by the invention has the advantages that the process of activating persulfate through a non-free radical direct electron transfer mode is milder, compared with the oxidation stress generated by free radicals, the bismuth carbon-embedded catalyst can reduce the generation of byproducts, reduce the influence on other beneficial substances in a water body, and effectively reduce the risks of the environment and human bodies. The method does not need irradiation treatment of visible light, has higher catalytic activity, and can more effectively sterilize and disinfect specific structures and metabolic processes of target microorganisms, thereby improving the treatment efficiency; the result shows that the bismuth carbon-embedded catalyst Bi@CC activation persulfate system has a bacterial inactivation rate of nearly 100% after being sterilized for 35min by 6.5log ₁₀ cfu/mL of escherichia coli (E.coli K-12) solution.

In some embodiments, the persulfate is present in an amount of from 0.5 to 2mM and the activated persulfate catalyst is present in an amount of from 0.5 to 2mg/mL.

In some embodiments, the bacteria that are sterilized include staphylococcus aureus, escherichia coli, and bacillus.

Compared with the prior art, the invention has the beneficial effects that:

The invention provides an activated persulfate catalyst, which is prepared by bismuth salt and acyl benzene ligands, and then Bi-MOFs are calcined in situ, the calcining temperature is controlled, bi microspheres are connected in a carbon layer, and Bi microspheres are combined with the interface of the carbon layer to form Bi-C bonds, so that the bismuth carbon-embedded catalyst with a chain A structure is obtained. The bismuth carbon-embedded catalyst with the chain A structure can activate persulfate through a non-free radical direct electron transfer path, and has higher activity and selectivity.

The invention provides an application of an activated persulfate catalyst in sterilizing and disinfecting the activated persulfate, which activates the persulfate through a non-free radical direct electron transfer path, has higher sterilization efficiency, and solves the problem that more byproducts are generated when the persulfate is activated through a free radical path. The activated persulfate catalyst activated persulfate can have higher bacterial inactivation rate on bacteria such as staphylococcus aureus, escherichia coli, bacillus and the like, wherein the bacterial inactivation rate is nearly 100% after the activated persulfate catalyst activated persulfate system is sterilized for 35min on 6.5log10cfu/mL escherichia coli (E.coli K-12) solution.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) image of the Bi@CC material of example 1. Fig. 1 (b) is a partial enlarged view of fig. 1 (a).

Fig. 2 is a Transmission Electron Microscope (TEM) image of the bi@cc material of example 1. Fig. 2 (b) is a partial enlarged view of fig. 2 (a).

Fig. 3 is an X-ray diffraction (XRD) pattern of different materials.

FIG. 4 is a graph showing the results of the quenching experiments of the present invention.

FIG. 5 is a graph comparing the bactericidal performance of various catalysts of the present invention activated persulfate.

FIG. 6 is a graph comparing the bactericidal performance of the catalyst activated persulfate of the present invention against different strains.

FIG. 7 is a graph showing the bactericidal properties of the catalysts of the present invention for activating persulfate at different catalyst dosages.

FIG. 8 is a graph of the bactericidal properties of the catalyst of the present invention with different dosages of active persulfate.

Detailed Description

The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.

Example 1

The preparation method of the activated persulfate catalyst comprises the following steps:

S1, dissolving Bi (NO ₃)₃·5H₂ O (0.382 g,0.98 mmol) and H ₃ BTC (0.3836 g,1.84 mmol) in 20mL of mixed solvent for 20min, wherein the mixed solvent is a solution of DMF and methanol mixed according to a volume ratio of 1:3, carrying out hydrothermal reaction at 120 ℃ for 5H, centrifuging, collecting precipitate, washing with methanol for three times, and placing the precipitate in a vacuum drying oven, and drying at 60 ℃ for 12H to obtain Bi-MOFs;

S2, calcining the Bi-MOFs at 600 ℃ for 2 hours under the N ₂ atmosphere, wherein the heating rate is 5 ℃/min, after carbonization, slowly cooling black powder for 3 hours under the N ₂ atmosphere, cooling to room temperature, and taking out a sample to obtain the bismuth carbon-embedded catalyst, which is named Bi@CC.

Example 2

S1, dissolving Bi (NO ₃)₃·5H₂ O (0.382 g,0.98 mmol) and H ₃ BTC (0.3836 g,1.84 mmol) in 20mL of mixed solvent for 20min, wherein the mixed solvent is a solution of DMF and methanol mixed according to a volume ratio of 1:3, carrying out hydrothermal reaction at 110 ℃ for 6H, centrifuging, collecting precipitate, washing with methanol for three times, and placing the precipitate in a vacuum drying oven, and drying at 60 ℃ for 12H to obtain Bi-MOFs;

S2, calcining the Bi-MOFs at 550 ℃ for 2 hours under the N ₂ atmosphere, wherein the heating rate is 3 ℃/min, after carbonization, slowly cooling black powder for 3 hours under the N ₂ atmosphere, cooling to room temperature, and taking out a sample to obtain the bismuth carbon-embedded catalyst, which is named Bi@CC-2.

Example 3

S1, dissolving Bi (NO ₃)₃·5H₂ O (0.470 g,0.98 mmol) and phthalimide (0.302 g,1.84 mmol) in 20mL of mixed solvent for 20min by ultrasonic treatment, wherein the mixed solvent is a solution of DMF and methanol mixed according to a volume ratio of 1:3, carrying out hydrothermal reaction at 120 ℃ for 5h, centrifuging, collecting precipitate, washing with methanol for three times, and placing the precipitate in a vacuum drying oven, and drying at 60 ℃ for 12h to obtain Bi-MOFs;

S2, calcining the Bi-MOFs at 600 ℃ for 2 hours under the N ₂ atmosphere, wherein the heating rate is 5 ℃/min, after carbonization, slowly cooling black powder for 3 hours under the N ₂ atmosphere, cooling to room temperature, and taking out a sample to obtain the bismuth carbon-embedded catalyst, which is named Bi@CC-3.

Example 4

S2, calcining the Bi-MOFs at 600 ℃ for 2 hours in the N ₂ atmosphere, wherein the heating rate is 10 ℃/min, after carbonization, slowly cooling black powder for 3 hours in the N ₂ atmosphere, cooling to room temperature, and taking out a sample to obtain the bismuth carbon-embedded catalyst, which is named Bi@CC.

In the preparation process of the catalyst, the temperature rising rate is too high, the local temperature gradient is large, the carbonization is uneven, the connectivity between Bi and carbon layers is influenced, and the morphology and the dimensional stability of the Bi microspheres are influenced

Example 5

The bismuth carbon-inlaid catalyst is applied to the sterilization and disinfection of activated persulfates, the Bi@CC catalyst (1 mg/mL) prepared in example 1 is mixed with a persulfates solution (1 mM), and the mixture is applied to the inactivation of escherichia coli (E.coli K-12).

Example 6

The bismuth carbon-inlaid catalyst is used for activating persulfate sterilization and disinfection, and the Bi@CC catalyst (1 mg/mL) prepared in example 1 is mixed with persulfate solution (1 mM) to be used for inactivating staphylococcus aureus (S.aureus).

Example 7

The bismuth carbon-inlaid catalyst is used for activating persulfate sterilization and disinfection, and the Bi@CC catalyst (1 mg/mL) prepared in example 1 is mixed with persulfate solution (1 mM) to inactivate bacillus megaterium (BM 1-1).

Example 8

The use of a bismuth-intercalated catalyst for the sterilization and disinfection of activated persulfates was substantially the same as in example 5, except that: the concentration of the Bi@CC catalyst was 0.5mg/mL.

Example 9

The use of a bismuth-intercalated catalyst for the sterilization and disinfection of activated persulfates was substantially the same as in example 5, except that: the concentration of the Bi@CC catalyst was 2mg/mL.

Example 10

The use of a bismuth-intercalated catalyst for the sterilization and disinfection of activated persulfates was substantially the same as in example 5, except that: the concentration of persulfate was 0.5mg/mL.

Example 11

The use of a bismuth-intercalated catalyst for the sterilization and disinfection of activated persulfates was substantially the same as in example 5, except that: the concentration of persulfate was 2mg/mL.

Comparative example 1

A method for sterilizing and disinfecting by activated persulfate, which is different from example 5 in that: the catalyst used for activating the persulfate in this comparative example was pure carbon (C).

The preparation method of the pure carbon comprises the following steps: the Bi@CC catalyst prepared in example 5 is etched for 12 hours by using 1mol/L hydrofluoric acid, washed to be neutral by using ultrapure water, and dried for 12 hours at 60 ℃, and the obtained material is pure carbon.

Comparative example 2

A method for sterilizing and disinfecting by activated persulfate, which is different from example 5 in that: the catalyst used for the activation of persulfate in this comparative example was bismuth powder (Bi), with an average particle diameter of 50 μm, and a purity of 99.99% purchased from Shanghai Ala Ding Shenghua technology Co., ltd.

Comparative example 3

A method for sterilizing and disinfecting by activated persulfate, which is different from example 5 in that: the catalyst used for activating the persulfate in this comparative example was a mixture of pure carbon (C) and bismuth powder (Bi) and was ultrasonically dispersed for 20 minutes, wherein the molar ratio of C to Bi was 16.6:1.

The bismuth powder (Bi) has an average particle diameter of 50 μm and a purity of 99.99% purchased from Shanghai Ala Ding Shenghua technologies Co.

Comparative example 4

A method for sterilizing and disinfecting by activated persulfate, which is different from example 5 in that: the preparation method of the bismuth carbon-embedded catalyst of the comparative example comprises the following steps:

S2, calcining the Bi-MOFs at 800 ℃ for 2 hours in the N ₂ atmosphere, wherein the heating rate is 5 ℃/min, after carbonization, slowly cooling black powder for 3 hours in the N ₂ atmosphere, cooling to room temperature, and taking out a sample to obtain the bismuth carbon-embedded catalyst, which is marked as Bi@CC.

Performance testing

1. Scanning Electron Microscope (SEM) detection

The Bi@CC material prepared in example 1 is subjected to scanning electron microscope SEM detection, and the detection result is shown in FIG. 1.

As can be seen from the graph, the Bi@CC material is in the form of a 2D rod-shaped carbon frame, and the average length is 20 mu m; and the bismuth nanospheres are embedded in the carbon framework and on the surface, and the average diameter is about 25nm.

2. Transmission Electron Microscope (TEM) detection

The Bi@CC material prepared in example 1 was subjected to Transmission Electron Microscopy (TEM) detection, and the detection result is shown in FIG. 2.

From the figure, transmission electron microscope imaging proves that the Bi nanospheres are inserted into the carbon framework to form the catalyst of chain mail structure.

3. X-ray diffraction (XRD) detection

The Bi@CC material prepared in example 1 and the bismuth powder prepared in comparative example 2 are subjected to scanning electron microscope XRD detection respectively, and the detection results are shown in figure 3.

As can be seen from the graph, the positions of characteristic diffraction peaks in XRD patterns of the Bi@CC material and the bismuth powder are the same as those of Bi standard cards (Bi#85-1329), and the Bi@CC material and the bismuth powder are proved to contain simple substance Bi.

4. Quenching experiments

The experimental method comprises the following steps: in the bismuth-intercalated catalyst-activated persulfate sterilization and disinfection system of example 5, quenchers (0.1M) of different active species were added separately: 2, 6-tetramethylpiperidine-1-oxide (TEMPOL), furfuryl alcohol (FFA), t-butyl alcohol (TBA), methanol (Methanol), K ₂Cr₂O₇, the above quenchers were used for quenching-O ₂ ^-、¹O₂, -OH and-OH, respectivelyE ^-; after the end of the experiment, the bactericidal effect after addition of the quencher was calculated.

Detection result: as shown in fig. 4.

As can be seen, capture with Methanol resulted in OH andAfter quenching, the sterilization effect was observed to be only reduced by 0.9log ₁₀ cfu/mL compared to the No-quencher addition (No scavenger curve); when TBA is used as an OH trapping agent, the sterilization effect is inhibited by 0.4log ₁₀ cfu/ml; i.e.After being quenched, the sterilization effect is reduced by 0.5log ₁₀ cfu/mL; the above description of OH and/orIs not the primary active species of the system. Similarly, the capture experiments using TEMPOL showed that O ₂ ^- has limited contribution to the disinfection process, inhibiting only the bactericidal effect of 1.03log ₁₀ cfu/ml. Using FFA (Furfuryl alcohol) as ¹O₂ trap there was little change in the effectiveness of the sterilization system compared to the original sterilization system, indicating that ¹O₂ is still not a major active ingredient. However, the sterilization effect of 4.8log ₁₀ cfu/ml was inhibited by quenching the electrons with K ₂Cr₂O₇, indicating that electrons are the primary active species during sterilization.

Based on the above analysis, it can be concluded that: the sterilization system of the Bi@CC catalyst is mainly carried out by a non-radical route, wherein the sterilization system comprises electron conduction and electron transfer processes. The Bi@CC catalyst is proved to activate PS by adopting a non-free radical direct electron transfer path.

5. Detection of sterilization performance of persulfate activated by different catalysts

(1) The Bi@CC material prepared in example 1, the pure carbon of comparative example 1 and the bismuth powder of comparative example 2 were taken as catalyst samples, and the catalyst samples and persulfate were added to a solution containing 6.5log ₁₀ cfu/mL of E.coli (E.coli K-12) at a concentration of 1mg/mL and a concentration of 1mM of persulfate, and the activity of E.coli at different times was measured, and the results are shown in FIG. 5.

From the graph, the Bi@CC catalyst activated persulfate can be almost completely inactivated within 35 minutes, and the bacterial inactivation rate is nearly 100%. When the pure carbon of comparative example 1 was used as the catalyst to activate persulfate, the E.coli activity was inactivated from the initial 6.52log ₁₀ cfu/mL to 4.17log ₁₀ cfu/mL after 35 minutes, and the bacterial inactivation concentration was 2.35log ₁₀ cfu/mL. When the bismuth powder of comparative example 2 was used as the catalyst to activate persulfate, the activity of Escherichia coli was inactivated from the initial 6.53log ₁₀ cfu/mL to 3.78log ₁₀ cfu/mL or more after 35 minutes, and the bacteria inactivation concentration was 2.75log ₁₀ cfu/mL.

(2) Samples of the catalysts of examples 2-4 and comparative examples 3-4 were taken and subjected to the active persulfate sterilization test using the method described in experiment (1) above; the results showed that the catalyst of example 2 activated persulfate for 35 minutes had a bacterial inactivation rate of 95%; example 3 the bacterial deactivation rate was 91.5% at 35 minutes of catalyst activated persulfate reaction; the catalyst obtained by the preparation method has excellent persulfate activation effect, and the bacterial inactivation rate is about 90% when the persulfate activation is carried out for 35 minutes; in the embodiment 4, when the catalyst is subjected to the activation persulfate reaction for 35 minutes, the bacterial inactivation concentration is not lower than 3.7log10 cfu/mL, and the bismuth carbon-embedded catalyst activation persulfate has higher bacterial inactivation rate to escherichia coli.

When the simple mixed catalytic activation persulfate of C and Bi in comparative example 3 was reacted for 35 minutes, E.coli was inactivated from the initial 6.54log ₁₀ cfu/mL to 4.3log ₁₀ cfu/mL at a bacterial inactivation concentration of 2.35log ₁₀ cfu/mL; the calcination temperature during the preparation of the catalyst of comparative example 4 was too high, resulting in incomplete interfacial bonding of Bi microspheres and carbon layers, and when the persulfate activation reaction was performed for 35 minutes, E.coli was inactivated from the initial 6.5log ₁₀ cfu/mL to 3.2log ₁₀ cfu/mL, and the bacteria inactivation concentration was 0.3log ₁₀ cfu/mL.

6. Sterilization performance detection of different strains

The application sterilization performance of the bismuth-embedded carbon catalysts of examples 4-6 in the sterilization and disinfection of the activated persulfate is detected, and the specific steps are as follows: the Bi@CC material of example 1 and persulfate were added to an E.coli (E.coli K-12) solution, a Staphylococcus aureus (S.aureus) solution and a Bacillus megaterium (BM 1-1) solution each containing 6.5 logs ₁₀ cfu/mL of bacteria, and the Bi@CC catalyst content was 1mg/mL and the persulfate solution content was 1mM, and the results are shown in FIG. 6.

From the graph, the Bi@CC catalyst of the invention activates persulfate to enable the strain to be almost completely inactivated in 45 minutes; wherein, aiming at escherichia coli (E.coli K-12) and bacillus megaterium (BM 1-1), the Bi@CC catalyst activated persulfate can be almost completely inactivated within 35 minutes; for staphylococcus aureus (s.aureus) nearly complete inactivation was achieved 45 minutes after activation of persulfate.

7. Sterilization performance detection of different catalyst dosages

A solution containing 7.0log ₁₀ cfu/mL of E.coli (E.coli K-12) was reacted for 35min by the method of examples 4, 7-8, and the results are shown in FIG. 7.

As can be seen from the graph, when the dosage of the Bi@CC catalyst is 0.5mg/mL, the cell concentration damage of escherichia coli after persulfate is activated is 2.5log ₁₀ cfu/mL; when the dosage of the Bi@CC catalyst is more than 1.0mg/mL, the damage of the cell concentration is 6.5log ₁₀ cfu/mL; when the dosage of the Bi@CC catalyst is more than 2.0mg/mL, the damage of the cell concentration is 6.83log ₁₀ cfu/mL. The above shows that the Bi@CC catalyst provided by the invention has better activity of sterilizing persulfate at a lower dosage (1.0 mg/mL).

8. Sterilization performance detection of different persulfate doses

A solution containing 7.0log ₁₀ cfu/mL of E.coli (E.coli K-12) was reacted for 35min by the method of examples 4, 9-10, and the results are shown in FIG. 8.

As can be seen, the cell loss concentration was 2.79log ₁₀ cfu/mL at the persulfate dose of 0.5 mg/mL; the concentration of cell loss was 6.49log ₁₀ cfu/mL at the dose of persulfate at 1.0 mg/mL; the persulfate was dosed at 2.0mg/mL with a cell loss concentration of 6.98log ₁₀ cfu/mL. The above shows that the Bi@CC catalyst provided by the invention also has better sterilization performance of activated persulfate when the dosage of persulfate is low (1.0 mg/mL).

The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims

1. The preparation method of the activated persulfate catalyst is characterized by comprising the following steps of:

2. The activated persulfate catalyst according to claim 1, characterized in that in step S2 of the preparation method, the calcination temperature is 550 to 650 ℃.

3. The activated persulfate catalyst according to claim 1, characterized in that in step S2 of the production method, the calcination time is 1.5 to 3 hours and the temperature rising rate is 3 to 7 ℃/min.

4. The activated persulfate catalyst according to claim 1, characterized in that in step S1 of the production process, the molar ratio of the bismuth salt to the acylbenzene ligand is 1: (1.5-2.5).

5. The activated persulfate catalyst of claim 1 or 4 wherein the acylbenzene ligand is at least one of trimesic acid, terephthalic acid, and a phthalimide.

6. The activated persulfate catalyst according to claim 1, characterized in that in step S1 of the production process, the reaction temperature of the hydrothermal reaction is 110 to 130 ℃ and the reaction time is 4 to 6 hours.

7. A method for preparing an activated persulfate catalyst, comprising the steps of:

8. Use of an activated persulfate catalyst as defined in any one of claims 1 to 6 for the sterilization and disinfection of activated persulfate.

9. The use according to claim 8, wherein the persulfate is used in an amount of 0.5 to 2mM and the activated persulfate catalyst is used in an amount of 0.5 to 2mg/mL.

10. The use according to claim 8, wherein the bacteria for sterilization and disinfection comprise staphylococcus aureus, escherichia coli and bacillus.