An activated persulfate catalyst, its preparation method and application

Abstract

The application 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 intercalation catalyst in a chain structure, and the preparation method comprises the following steps: S1, taking a bismuth salt and an acyl benzene ligand as reaction substrates, and synthesizing Bi-MOFs through a hydrothermal reaction; and S2, calcining the Bi-MOFs at 500-700 DEG C under an inert gas atmosphere to obtain the bismuth-carbon intercalation catalyst.The bismuth-carbon intercalation catalyst activates persulfate through a non-radical direct electron transfer path, has higher activity and selectivity, can more effectively sterilize and disinfect specific structures and metabolic processes of target microorganisms, and improves the treatment efficiency; and can reduce the generation of by-products, effectively reduces the risk of the environment and the human body.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst technology, more particularly, to an activated persulfate catalyst and its preparation method and application. BACKGROUND

[0002] With the acceleration of modern life pace and the improvement of people's health consciousness, water treatment disinfection and sterilization technology has gradually become an important research field. However, traditional water treatment disinfection and sterilization technology often has some defects, which affects its effect and reliability in practical application. First of all, traditional disinfection and sterilization technology often needs a long processing time and a complex process. For example, chlorine disinfection technology needs to add chlorine solution into water and react for a certain time, which leads to long disinfection and sterilization time, complex process and easy to produce by-products. Secondly, some disinfectants will produce toxic substances during disinfection, which will pose potential risks to the environment and human health. For example, the use of disinfectants containing halogenated methane and other substances will increase the carcinogenic substances such as halogenated methane, further increasing the difficulty and risk of water treatment. Finally, traditional water treatment disinfection and sterilization technology often has reliability and stability problems. For example, ultraviolet disinfection technology has poor adaptability to various water qualities, and is easily affected by color and turbidity, which greatly limits its disinfection effect. Therefore, in order to solve the shortcomings of traditional water treatment disinfection and sterilization technology, new, more effective, safe, reliable and environmentally friendly technology needs to be developed. The characteristics and advantages of various technologies need to be further explored and applied to practical application scenarios to improve the efficiency, reliability and safety of water treatment disinfection and sterilization technology and protect people's life and health safety.

[0003] As a new water treatment disinfection and sterilization technology, persulfate advanced oxidation technology has many advantages that traditional technology does not have. Persulfate can be stored stably under normal environmental conditions and is not easy to decompose, volatilize or be affected by other substances, making it more convenient in practical application. This advantage makes persulfate advanced oxidation technology widely used in modern water treatment engineering.

[0004] Patent CN113600173A proposes the application of bismuth catalyst in activating persulfate sterilization and disinfection. In this reaction system, persulfate and bismuth catalyst contact with each other, persulfate is activated to produce hydroxyl radical (·OH), sulfate radical Superoxide radical (·O2 - ), singlet oxygen ( 1 O2) and other free radical species, which attack target bacteria, causing cell wall rupture and DNA leakage, and ultimately leading to death. However, on the one hand, the efficiency of bismuth catalyst in activating persulfate sterilization and disinfection is low, and the activated persulfate has a concentration of 7log 10The sterilization number is only 0.9-5.87log after 30min treatment of E. coli with 1000cfu / mL 10 The sterilization efficiency is improved by further activating persulfate under visible light (λ≥420nm) irradiation, and the light-assisted activation causes energy waste; on the other hand, the reaction system activates persulfate through a free radical path, and the free radical path has low activation selectivity and generates more byproducts, which means that a large amount of toxic and harmful substances are generated in the sterilization process, and other beneficial substances in the water body are affected, which has a great risk to the environment and human body. SUMMARY

[0005] The purpose of the present application is to overcome the defects and deficiencies of the existing bismuth catalyst in activating the persulfate system through a free radical path, and to provide an activated persulfate catalyst which has a chain-methyl structure and can activate persulfate through a non-free radical direct electron transfer path, and has higher catalytic activity and selectivity.

[0006] Another purpose of the present application is to provide a preparation method of the activated persulfate catalyst.

[0007] Another purpose of the present application is to provide an application of the activated persulfate catalyst in activating persulfate sterilization, which activates persulfate through a non-free radical direct electron transfer path, has higher catalytic activity and selectivity, and improves the sterilization efficiency of activated persulfate.

[0008] The above purposes of the present application are achieved by the following technical solutions:

[0009] The present application protects an activated persulfate catalyst, which is a bismuth-carbon intercalation catalyst with a chain-methyl structure, and a preparation method of the activated persulfate catalyst, comprising the following steps:

[0010] S1, Bi-MOFs are synthesized by hydrothermal reaction of bismuth salt and acyl benzene ligand as reaction substrates;

[0011] S2, the Bi-MOFs are calcined at 500-700 DEG C under inert gas atmosphere to obtain the activated persulfate catalyst.

[0012] The activated persulfate catalyst of the present application uses bismuth salt and acyl benzene ligand to prepare Bi-MOFs, and then in-situ calcines Bi-MOFs and controls the calcination temperature, so that Bi microspheres are connected in the carbon layer, the interface of Bi microspheres and carbon layer is combined to form Bi-C bond, and a bismuth-carbon intercalation catalyst with a chain-methyl structure is obtained.

[0013] On one hand, the bismuth-embedded carbon catalyst can activate persulfate through a non-radical direct electron transfer pathway, thereby improving the disinfection efficiency of activated persulfate; the principle is that: based on the interface combination of Bi microspheres and carbon layers to form Bi-C bonds, the electron rearrangement between the bismuth ball and the carbon layer makes it have an electronic metal-support interaction (EMSI), and the electron is transferred from Bi to the carbon layer through the EMSI coordination structure of Bi-C, and the electron rearrangement of Bi-C is conducive to the formation of an intermediate complex (cat-PS*) with persulfate (PS) to cause higher activation function, enhance the dominant electron transfer pathway (ETP) process of the system, and intensify the damage to cells. Moreover, the bismuth-embedded carbon itself can also cause damage to bacteria through extracellular electron transfer, and a small amount of free radicals generated in the system can also cause damage to bacteria. On the other hand, the bismuth-embedded carbon catalyst has stronger stability and is not prone to metal ion leakage, and has good cycle performance and safety.

[0014] In the preparation method of the bismuth-embedded carbon catalyst, the calcination temperature (500-700℃) needs to be accurately controlled to ensure that the interface combination between the Bi microspheres and the carbon layer is good, so as to effectively form the Bi-C bond and improve the stability and catalytic performance of the material. If the calcination temperature is too high, the carbon layer may be sintered or the structure may change, so that the interface combination between the Bi microspheres and the carbon layer is not complete or decomposition occurs, thereby affecting the formation of the Bi-C bond and weakening the stability and catalytic performance of the material. Conversely, if the calcination temperature is too low, the interface combination between the Bi microspheres and the carbon layer may not be completely achieved, thereby affecting the formation of the Bi-C bond and reducing the stability and catalytic performance of the material.

[0015] In some embodiments, in step S2 of the preparation method, the calcination temperature is 550-650℃. The interface combination between the Bi microspheres and the carbon layer is better. Preferably, when the calcination temperature is 600±10℃, the catalyst has more significant catalytic performance.

[0016] In some embodiments, in step S2 of the preparation method, the calcination time is 1.5-3h, and the heating rate is 3-7℃ / min. Controlling the heating rate is beneficial to improving the stability of the catalyst; if the heating rate is too high, the local temperature gradient will be large, causing uneven carbonization, affecting the connectivity between Bi and the carbon layer, and affecting the morphology and size stability of the Bi microspheres; if the heating rate is too low, the carbonization reaction will be slow, which may cause insufficient carbonization in some areas and be insufficient to promote the formation and perfection of the Bi microspheres, thereby affecting the formation of the Bi-C bond and ultimately affecting the morphology and catalytic performance of the Bi@CC material. Preferably, the heating rate is 4-6℃ / min, and the Bi@CC material has good morphology and catalytic performance.

[0017] In some embodiments, the molar ratio of the bismuth salt and the acyl benzene ligand in step S1 of the preparation method is 1:(1.5-2.5).

[0018] In some embodiments, the acyl benzene ligand is at least one of trimesic acid, terephthalic acid, and phthaloyl diamine. Preferably, when the acyl benzene ligand is trimesic acid (H3BTC), the bismuth carbon intercalation catalyst has higher catalytic performance.

[0019] In some embodiments, the bismuth salt is at least one of bismuth nitrate pentahydrate, bismuth chloride, and bismuth nitrate.

[0020] In some embodiments, the reaction temperature of the hydrothermal reaction in step S1 of the preparation method is 110-130°C, and the reaction time is 4-6h.

[0021] The present application protects a preparation method of an activated persulfate catalyst, comprising the following steps:

[0022] S1, using a bismuth salt and an acyl benzene ligand as reaction substrates, and synthesizing Bi-MOFs through a hydrothermal reaction;

[0023] S2, calcining the Bi-MOFs at 500-700°C under an inert gas atmosphere to obtain the bismuth carbon intercalation catalyst.

[0024] The present application protects the application of an activated persulfate catalyst in activated persulfate sterilization and disinfection.

[0025] The bismuth carbon intercalation catalyst of the present application has a chain structure, which can activate persulfate through a non-radical direct electron transfer path. Compared with the existing radical path activated persulfate sterilization and disinfection system, the process of activating persulfate through the non-radical direct electron transfer method of the bismuth carbon intercalation catalyst of the present application is more gentle, and compared with the oxidative stress generated by radicals, it can reduce the generation of by-products and reduce the impact on other beneficial substances in the water body, effectively reducing the risk to the environment and the human body. It does not require visible light irradiation treatment, and has higher catalytic activity, and can more effectively sterilize and disinfect specific structures and metabolic processes of target microorganisms, improving the treatment efficiency. The results show that the bismuth carbon intercalation catalyst Bi@CC activated persulfate system of the present application has a bacterial inactivation rate of nearly 100% after sterilizing a 6.5 log 10 cfu / mL E. coli (E. coli K-12) solution for 35 min.

[0026] In some embodiments, the dosage of the persulfate is 0.5-2mM, and the dosage of the activated persulfate catalyst is 0.5-2mg / mL.

[0027] In some embodiments, the bacteria killed by the sterilization and disinfection include Staphylococcus aureus, Escherichia coli and Bacillus.

[0028] Compared with the prior art, the application has the following beneficial effects:

[0029] The application provides a persulfate-activating catalyst, Bi-MOFs are prepared by using a bismuth salt and an acyl benzene ligand, the Bi-MOFs are calcined in situ and the calcination temperature is controlled, so that Bi microspheres are connected in a carbon layer, the interface of the Bi microspheres and the carbon layer is combined to form a Bi-C bond, and a bismuth-carbon catalyst with a chain-matter structure is obtained. The bismuth-carbon catalyst with the chain-matter structure can activate persulfate through a non-radical direct electron transfer path, and has higher activity and selectivity.

[0030] The application provides an application of the persulfate-activating catalyst in sterilization and disinfection of bacteria by activating persulfate, and the persulfate is activated through a non-radical direct electron transfer path, so that higher sterilization efficiency is achieved, and the problem of more by-products generated when the persulfate is activated through a radical path is overcome. The persulfate activated by the persulfate-activating catalyst can have a high bacteria inactivation rate on bacteria such as Staphylococcus aureus, Escherichia coli and Bacillus, and the persulfate activated by the persulfate-activating catalyst of the application can have a bacteria inactivation rate of nearly 100% on 6.5log10cfu / mL of an E.coli K-12 solution after sterilization for 35 min. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Figure 1 is a scanning electron microscope (SEM) image of the Bi@CC material of Example 1, wherein, Figure 1 Figure 1 (b) is a partial enlarged view of Figure 1 (a). Figure 1 Figure 1 (b) is a partial enlarged view of Figure 1 (a).

[0032] Figure 2 Figure 2 is a transmission electron microscope (TEM) image of the Bi@CC material of Example 1, wherein, Figure 2 Figure 2 (b) is a partial enlarged view of Figure 2 (a). Figure 2 Figure 2 (b) is a partial enlarged view of Figure 2 (a).

[0033] Figure 3 Figure 3 is an X-ray diffraction (XRD) image of different materials.

[0034] Figure 4 Figure 4 is a result image of the quenching experiment of the application.

[0035] Figure 5 Figure 5 is a comparison image of sterilization performance of different catalysts activating persulfate.

[0036] Figure 6 Figure 6 is a comparison image of sterilization performance of different bacteria by the catalyst activating persulfate.

[0037] Figure 7 Figure for bactericidal performance of the catalyst of the present application under different catalyst dosages to activate persulfate.

[0038] Figure 8 Figure for bactericidal performance of the catalyst of the present application under different catalyst dosages to activate persulfate. DETAILED DESCRIPTION

[0039] The present application will be further described in conjunction with specific embodiments, but the embodiments do not limit the present application in any form. Unless otherwise specified, the raw materials used in the embodiments of the present application are commercially available raw materials.

[0040] Example 1

[0041] A preparation method of an activated persulfate catalyst is as follows:

[0042] S1, Bi(NO3)3·5H2O (0.472 g, 0.98 mmol) and H3BTC (0.386 g, 1.84 mmol) were dissolved in 20 mL of a mixed solvent, which was a solution of DMF and methanol mixed at a volume ratio of 1:3, under ultrasonic for 20 min, followed by hydrothermal reaction at 120℃ for 5 h, centrifugation and collection of the precipitate, washing with methanol for three times, and placing it in a vacuum drying box, drying at 60℃ for 12 h, to obtain Bi-MOFs;

[0043] S2, the Bi-MOFs were calcined at 600℃ for 2 h under N2 atmosphere, with a heating rate of 5℃ / min, after carbonization, the black powder was slowly cooled for 3 hours under N2 atmosphere, after cooling to room temperature, the sample was taken out, to obtain a bismuth-carbon catalyst, denoted as Bi@CC.

[0044] Example 2

[0045] A preparation method of an activated persulfate catalyst is as follows:

[0046] S1, Bi(NO3)3·5H2O (0.472 g, 0.98 mmol) and H3BTC (0.386 g, 1.84 mmol) were dissolved in 20 mL of a mixed solvent, which was a solution of DMF and methanol mixed at a volume ratio of 1:3, under ultrasonic for 20 min, followed by hydrothermal reaction at 120℃ for 5 h, centrifugation and collection of the precipitate, washing with methanol for three times, and placing it in a vacuum drying box, drying at 60℃ for 12 h, to obtain Bi-MOFs;

[0047] S2, the Bi-MOFs were calcined at 550℃ for 2h under N2 atmosphere, the heating rate was 3℃ / min, after carbonization, the black powder was slowly cooled for 3 hours under N2 atmosphere, after cooling to room temperature, the sample was taken out, and a bismuth-embedded carbon catalyst was obtained, which was recorded as Bi@CC-2.

[0048] Example 3

[0049] A preparation method of an activated persulfate catalyst is as follows:

[0050] S1, Bi(NO3)3·5H2O (0.472 g, 0.98 mmol) and benzene dicarboxylic diamide (0.302 g, 1.84 mmol) were dissolved in 20 mL of a mixed solvent which was a solution of DMF and methanol mixed at a volume ratio of 1:3 under ultrasonic for 20 min, and then hydrothermal reaction was carried out at 120℃ for 5h, the precipitate was collected by centrifugation and washed with methanol for three times, and then placed in a vacuum drying box and dried at 60℃ for 12h, and Bi-MOFs were obtained;

[0051] S2, the Bi-MOFs were calcined at 600℃ for 2h under N2 atmosphere, the heating rate was 5℃ / min, after carbonization, the black powder was slowly cooled for 3 hours under N2 atmosphere, after cooling to room temperature, the sample was taken out, and a bismuth-embedded carbon catalyst was obtained, which was recorded as Bi@CC-3.

[0052] Example 4

[0053] A preparation method of an activated persulfate catalyst is as follows:

[0054] S1, Bi(NO3)3·5H2O (0.472 g, 0.98 mmol) and benzene dicarboxylic diamide (0.302 g, 1.84 mmol) were dissolved in 20 mL of a mixed solvent which was a solution of DMF and methanol mixed at a volume ratio of 1:3 under ultrasonic for 20 min, and then hydrothermal reaction was carried out at 120℃ for 5h, the precipitate was collected by centrifugation and washed with methanol for three times, and then placed in a vacuum drying box and dried at 60℃ for 12h, and Bi-MOFs were obtained;

[0055] S2, the Bi-MOFs were calcined at 600℃ for 2h under N2 atmosphere, the heating rate was 5℃ / min, after carbonization, the black powder was slowly cooled for 3 hours under N2 atmosphere, after cooling to room temperature, the sample was taken out, and a bismuth-embedded carbon catalyst was obtained, which was recorded as Bi@CC-3.

[0056] In the catalyst preparation process of the example, the heating rate is too high, the local temperature gradient is large, the carbonization is not uniform, the connection between Bi and the carbon layer is affected, and the morphology and size stability of the Bi microspheres are affected

[0057] Example 5

[0058] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, Bi@CC catalyst (1 mg / mL) prepared in Example 1 was mixed with a persulfate solution (1 mM) and applied to inactivate E. coli K-12.

[0059] Example 6

[0060] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, Bi@CC catalyst (1 mg / mL) prepared in Example 1 was mixed with a persulfate solution (1 mM) and applied to inactivate S. aureus.

[0061] Example 7

[0062] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, Bi@CC catalyst (1 mg / mL) prepared in Example 1 was mixed with a persulfate solution (1 mM) and applied to inactivate B. megaterium (BM1-1).

[0063] Example 8

[0064] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, which was basically the same as Example 5, except that the concentration of Bi@CC catalyst was 0.5 mg / mL.

[0065] Example 9

[0066] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, which was basically the same as Example 5, except that the concentration of Bi@CC catalyst was 2 mg / mL.

[0067] Example 10

[0068] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, which was basically the same as Example 5, except that the concentration of persulfate was 0.5 mg / mL.

[0069] Example 11

[0070] Application of a bismuth-embedded carbon catalyst in activating persulfate for sterilization and disinfection, which was basically the same as Example 5, except that the concentration of persulfate was 2 mg / mL.

[0071] Comparative Example 1

[0072] A method for activating persulfate for sterilization and disinfection, which was different from Example 5 in that the catalyst used to activate persulfate in this comparative example was pure carbon (C).

[0073] The preparation method of the pure carbon is as follows: the Bi@CC catalyst prepared in Example 5 is etched with 1 mol / L hydrofluoric acid for 12 h, washed with ultrapure water until neutral, and dried at 60°C for 12 h, and the obtained material is the pure carbon.

[0074] Comparative Example 2

[0075] A method for activating persulfate to sterilize and disinfect, which is different from Example 5 in that the catalyst for activating persulfate in the present comparative example is bismuth powder (Bi) with an average particle size of 50 μm and a purity of 99.99% purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.

[0076] Comparative Example 3

[0077] A method for activating persulfate to sterilize and disinfect, which is different from Example 5 in that the catalyst for activating persulfate in the present comparative example is a mixture of pure carbon (C) and bismuth powder (Bi) and is ultrasonically dispersed for 20 min, wherein the molar ratio of C to Bi is 16.6:1.

[0078] The preparation method of the pure carbon is as follows: the Bi@CC catalyst prepared in Example 5 is etched with 1 mol / L hydrofluoric acid for 12 h, washed with ultrapure water until neutral, and dried at 60°C for 12 h, and the obtained material is the pure carbon.

[0079] The bismuth powder (Bi) has an average particle size of 50 μm and a purity of 99.99% and is purchased from Shanghai Aldrin Biochemical Technology Co., Ltd.

[0080] Comparative Example 4

[0081] A method for activating persulfate to sterilize and disinfect, which is different from Example 5 in that the preparation method of the bismuth-embedded-carbon catalyst in the present comparative example is as follows:

[0082] S1, Bi(NO3)3·5H2O (0.472 g, 0.98 mmol) and H3BTC (0.386 g, 1.84 mmol) are dissolved in 20 mL of a mixed solvent which is a solution of DMF and methanol mixed in a volume ratio of 1:3 under ultrasonication for 20 min, followed by hydrothermal reaction at 120°C for 5 h, centrifugation and collection of the precipitate, washing with methanol for three times, and placing it in a vacuum drying oven for drying at 60°C for 12 h to obtain Bi-MOFs;

[0083] S2, the Bi-MOFs are calcined at 800°C for 2 h under N2 atmosphere at a temperature increasing rate of 5°C / min, and after carbonization, the black powder is slowly cooled under N2 atmosphere for 3 hours, and after cooling to room temperature, the sample is taken out to obtain the bismuth-embedded-carbon catalyst, which is recorded as Bi@CC.

[0084] Performance test

[0085] 1. Scanning electron microscopy (SEM) inspection

[0086] The Bi@CC material prepared in Example 1 was examined by scanning electron microscopy (SEM), and the results are as follows: Figure 1 As shown.

[0087] As shown in the figure, the Bi@CC material exhibits a 2D rod-shaped carbon framework morphology with an average length of 20 μm; and bismuth nanospheres are embedded inside and on the surface of the carbon framework, with an average diameter of approximately 25 nm.

[0088] 2. Transmission electron microscopy (TEM) detection

[0089] The Bi@CC material prepared in Example 1 was examined by transmission electron microscopy (TEM), and the results are as follows: Figure 2 As shown.

[0090] As shown in the figure, transmission electron microscopy imaging confirmed that Bi nanospheres were inserted into the carbon framework to form a chain-like catalyst.

[0091] 3. X-ray diffraction (XRD) detection

[0092] The Bi@CC material prepared in Example 1 and the bismuth powder in Comparative Example 2 were subjected to scanning electron microscopy (SEM) XRD analysis, and the results are as follows: Figure 3 As shown.

[0093] As shown in the figure, the positions of the characteristic diffraction peaks in the XRD patterns of Bi@CC material and bismuth powder are the same as those in the Bi standard card (Bi#85-1329), proving that both Bi@CC material and bismuth powder contain elemental Bi.

[0094] 4. Quenching Experiment

[0095] The experimental method was as follows: In the bismuth-carbon intercalated catalyst activated persulfate sterilization system of Example 5, quenchers (0.1M) of different active species were added respectively: 2,2,6,6-tetramethylpiperidine-1-oxide (TEMPOL), furfuryl alcohol (FFA), tert-butanol (TBA), methanol, and K2Cr2O7. These quenchers were used to quench O2. - , 1 O2, ·OH, ·OH and e - After the experiment, the bactericidal effect after adding the quenching agent was calculated.

[0096] Test results: such as Figure 4 As shown.

[0097] As shown in the figure, using methanol for capture causes ·OH and After being quenched, the sterilization effect was observed to be reduced by only 0.9 log compared with the case without scavenger (No scavenger curve) 10 ; while the TBA was used as the ·OH trapping agent, the sterilization effect was inhibited by 0.4 log 10 cfu / ml; that is After being quenched, the sterilization effect was reduced by 0.5 log 10 cfu / mL; the above indicates that ·OH and / or is not the main active species of the system. Similarly, the trapping experiment using TEMPOL shows that ·O2 - has a limited contribution to the disinfection process, and only inhibits the sterilization effect by 1.03 log 10 cfu / ml. Using FFA (Furfuryl alcohol) as 1 O2 trapping agent, the effectiveness of the sterilization system has almost no change compared with the original sterilization system, which indicates that 1 O2 is still not the main active component. However, by using K2Cr2O7 to quench electrons, the disinfection effect of 4.8 log 10 cfu / ml is inhibited, indicating that electrons are the main active substances in the sterilization process.

[0098] Based on the above analysis, it can be concluded that the sterilization system of the Bi@CC catalyst Bi@CC catalyst is mainly carried out through a non-radical pathway, which includes electron conduction and electron transfer process. It is proved that the Bi@CC catalyst activates PS by using a non-radical direct electron transfer path.

[0099] 5. Detection of sterilization performance of different catalysts for activating persulfate

[0100] (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, the catalyst samples and the persulfate were added to a solution containing 6.5 log 10 cfu / mL of E. coli K-12, the concentration of the catalyst sample in the solution was 1 mg / mL, the concentration of the persulfate was 1 mM, and the activity of the E. coli was detected at different times, and the results are shown in Figure 5 .

[0101] As can be seen from the figure, the Bi@CC catalyst of the application can activate the persulfate to be almost completely inactivated within 35 minutes, and the bacterial inactivation rate is nearly 100%. When the pure carbon of Comparative Example 1 is used as a catalyst to activate the persulfate, the activity of the E. coli is inactivated from 6.52 log 10 cfu / mL at the beginning to 4.17 log 10cfu / mL, the bacteria inactivation concentration was 2.35 log 10 cfu / mL. When the bismuth powder of Comparative Example 2 was used as a catalyst to activate persulfate, the E. coli activity was inactivated from 6.53 log 10 cfu / mL to 3.78 log 10 cfu / mL above, the bacteria inactivation concentration was 2.75 log 10 cfu / mL.

[0102] (2) Catalyst samples of Example 2-4 and Comparative Example 3-4 were taken and activated persulfate sterilization tests were performed using the method of (1) above; the results showed that the bacteria inactivation rate of the catalyst of Example 2 was 95% when activated persulfate for 35 minutes; the bacteria inactivation rate of the catalyst of Example 3 was 91.5% when activated persulfate for 35 minutes; it can be seen that the catalyst prepared by the method of the present application has excellent activated persulfate effect, and the bacteria inactivation rate is about 90% when activated persulfate for 35 minutes; the bacteria inactivation concentration of the catalyst of Example 4 was not less than 3.7 log10 cfu / mL when activated persulfate for 35 minutes, proving that the bismuth-carbon catalyst of the present application activated persulfate can have a high bacteria inactivation rate on E. coli.

[0103] The simple mixture of C and Bi in Comparative Example 3 activated persulfate for 35 minutes, and the E. coli was inactivated from 6.54 log 10 cfu / mL to 4.3 log 10 cfu / mL, the bacteria inactivation concentration was 2.35 log 10 cfu / mL; the catalyst of Comparative Example 4 was prepared at a too high calcination temperature, resulting in incomplete interface bonding between the Bi microspheres and the carbon layer, and the E. coli was inactivated from 6.5 log 10 cfu / mL to 3.2 log 10 cfu / mL, the bacteria inactivation concentration was 0.3 log 10 cfu / mL.

[0104] 6. Bactericidal performance detection of different bacteria

[0105] The bactericidal performance of the bismuth-carbon catalyst of Example 4-6 in activating persulfate sterilization and disinfection was detected, specifically: the Bi@CC material of Example 1 and persulfate were added to 6.5 log 10The results were obtained in solutions of *E. coli* (K-12) with cfu / mL bacteria, *S. aureus* (S. aureus) and *Bacillus megaterium* (BM1-1), with a Bi@CC catalyst concentration of 1 mg / mL and a persulfate concentration of 1 mM. Figure 6 As shown.

[0106] As shown in the figure, the Bi@CC catalyst of the present invention can nearly completely inactivate the bacterial strain within 45 minutes by activating persulfate; specifically, for Escherichia coli (E. coli K-12) and Bacillus megaterium (BM1-1), the Bi@CC catalyst of the present invention can nearly completely inactivate persulfate within 35 minutes; for Staphylococcus aureus, it is nearly completely inactivated after 45 minutes of persulfate activation.

[0107] 7. Sterilization performance testing with different catalyst dosages

[0108] The methods in Examples 4 and 7-8 were used to process 7.0 log... 10 The reaction was carried out with a solution of CFU / mL E. coli (E. coli K-12) for 35 min, and the results were as follows: Figure 7 As shown.

[0109] As shown in the figure, when the Bi@CC catalyst dosage is 0.5 mg / mL, the cell concentration of *E. coli* after activation by persulfate is reduced by 2.5 log [value missing]. 10 CFU / mL; When the Bi@CC catalyst dose is above 1.0 mg / mL, the cell concentration damage is 6.5 log [cfu / mL]. 10 CFU / mL; When the Bi@CC catalyst dose is above 2.0 mg / mL, the cell concentration damage is 6.83 log. 10 cfu / mL. This indicates that the Bi@CC catalyst of the present invention exhibits good activated persulfate bactericidal performance at a relatively low dose (1.0 mg / mL).

[0110] 8. Tests on the bactericidal performance of different persulfate dosages

[0111] The methods described in Examples 4 and 9-10 were used to process 7.0 log... 10 The reaction was carried out with a solution of CFU / mL E. coli (E. coli K-12) for 35 min, and the results were as follows: Figure 8 As shown.

[0112] As shown in the figure, when the persulfate dosage is 0.5 mg / mL, the cell loss concentration is 2.79 log₂O₅. 10 CFU / mL; when the persulfate dose was 1.0 mg / mL, the cell loss concentration was 6.49 log [value missing].10 cfu / mL; the cell loss concentration was 6.98 log when the dosage of persulfate was 2.0 mg / mL 10 cfu / mL. The above shows that the Bi@CC catalyst of the present application also has good activation of persulfate sterilization performance when the dosage of persulfate is low (1.0 mg / mL).

[0113] The above examples of the present application are merely examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can also be made by those of ordinary skill in the art. Here, it is not necessary and also impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. Use of an activated persulfate catalyst in activated persulfate germicidal disinfection, characterized in that, The activated persulfate catalyst is a bismuth-carbon intercalation catalyst in a chain structure, and a preparation method thereof includes the following steps: S1. Bi-MOFs are synthesized by hydrothermal reaction of a bismuth salt and an acyl benzene ligand as reaction substrates; the reaction temperature of the hydrothermal reaction is 110-130 DEG C, and the reaction time is 4-6 h; the acyl benzene ligand is at least one of trimesic acid, terephthalic acid, and phthaloyl diamine; S2. The Bi-MOFs are calcined at 500-700 DEG C under an inert gas atmosphere for 1.5-3 h to obtain the activated persulfate catalyst.

2. Use according to claim 1, characterized in that, In step S2 of the preparation method, the calcination temperature is 550-650 DEG C.

3. Use according to claim 1, characterized in that, In step S2 of the preparation method, the heating rate is 3-7 DEG C / min.

4. Use according to claim 1, characterized in that, In step S1 of the preparation method, the molar ratio of the bismuth salt to the acyl benzene ligand is 1:(1.5-2.5).

5. The use according to claim 1, characterized in that, The activated persulfate catalyst is in a 2D rod-shaped carbon framework morphology, with an average length of 20 µm; and bismuth nanospheres are intercalated in the interior and on the surface of the carbon framework, with an average diameter of 25 nm.

6. Use according to claim 1, characterized in that, The dosage of the persulfate is 0.5-2 mM, and the dosage of the activated persulfate catalyst is 0.5-2 mg / mL.

7. The use according to claim 1, characterized in that, The bacteria to be sterilized and disinfected include Staphylococcus aureus, Escherichia coli, and Bacillus sp.

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