阅读说明：本技术 铋催化剂在活化过硫酸盐杀菌消毒中的应用 (Application of bismuth catalyst in sterilization and disinfection by activating persulfate ) 是由 何春 陈诚 郑溪源 夏德华 陈琪 廖宇宏 屈伟 关心怡 于 2021-08-09 设计创作，主要内容包括：本发明属于环境功能材料技术领域,具体涉及铋催化剂在活化过硫酸盐杀菌消毒中的应用。选用铋系材料作为催化剂,活化过硫酸盐产生一系列具有高反应性的活性氧物种(ROS),攻击水体中的病原微生物,达到优异的杀菌消毒效果；在可见光照射条件还可以进一步提高消毒效率。并且,铋催化剂易于获取,成本较低,制备方法简单,具有较强的催化活性和较好的稳定性,活化过硫酸盐活化过硫酸盐杀菌消毒的方法操作简便,杀菌彻底、效率高,不产生消毒副产物；同时循环催化后,催化剂仍能保持较高的催化活性,也易于回收,并可通过再生重复使用,是环境友好型材料。(The invention belongs to the technical field of environmental functional materials, and particularly relates to an application of a bismuth catalyst in sterilization and disinfection by activating persulfate. Bismuth materials are selected as catalysts, persulfate is activated to generate a series of Reactive Oxygen Species (ROS) with high reactivity to attack pathogenic microorganisms in water, and excellent sterilization and disinfection effects are achieved; the sterilization efficiency can be further improved under the condition of visible light irradiation. In addition, the bismuth catalyst is easy to obtain, the cost is lower, the preparation method is simple, the catalyst has stronger catalytic activity and better stability, the method for activating persulfate and activating persulfate to sterilize and disinfect is simple and convenient to operate, the sterilization is thorough, the efficiency is high, and no disinfection by-product is generated; meanwhile, after the catalyst is circularly catalyzed, the catalyst still can keep higher catalytic activity, is easy to recover and can be repeatedly used through regeneration, and is an environment-friendly material.)

1. The application of the bismuth catalyst in sterilization and disinfection of activated persulfate is characterized in that the bismuth catalyst is simple substance bismuth or bismuth oxide, the use amount of the persulfate is 1.0-10.0 mM, and the use amount of the bismuth catalyst is 0.5-10.0 mg/mL.

2. The use according to claim 1, wherein the elemental bismuth is untreated elemental bismuth or elemental bismuth that has been treated with liquid nitrogen to form popcorn.

3. The use according to claim 2, wherein the popcorn-like elemental bismuth is prepared by a method comprising the steps of:

dissolving bismuth nitrate in nitric acid, fully stirring, adding ethylene glycol, and uniformly stirring; adding polyvinylpyrrolidone, stirring to completely disperse and dissolve the polyvinylpyrrolidone, performing hydrothermal reaction at 160-220 ℃, performing solid-liquid separation on the reaction liquid after complete reaction, and cleaning and drying the obtained solid to obtain simple substance bismuth; and treating the obtained simple substance bismuth by liquid nitrogen to obtain the bismuth-bismuth alloy.

4. The use according to claim 3, wherein the polyvinylpyrrolidone has a relative molecular mass of 24000 to 40000.

5. The application of claim 3, wherein the reaction time of the hydrothermal reaction is 8-48 h.

6. The use according to claim 3, wherein the time of the liquid nitrogen treatment is 10-60 min.

7. The use of claim 1, wherein the bismuth oxide is bismuth oxide or bismuth oxyhalide.

8. Use according to claim 1, wherein the persulfate is a peroxymonosulfate or peroxydisulfate.

9. The use of claim 1, wherein the bacteria to be sterilized comprise Escherichia coli, Staphylococcus aureus, Salmonella, and enterococcus faecalis.

10. The application of the bismuth-containing catalyst as claimed in claim 1, wherein when the bismuth-containing catalyst is used for activating persulfate to sterilize and disinfect, visible light irradiation is increased, and the irradiation condition of the visible light is that lambda is more than or equal to 420 nm.

Technical Field

The invention belongs to the technical field of environment functional materials. More particularly, it relates to the application of bismuth catalyst in the sterilization and disinfection of activated persulfate.

Background

Water shortage and pollution are one of the major challenges facing mankind in today's world. The regeneration and recovery of urban wastewater is an important way to relieve the problem of water shortage. However, a large amount of pathogenic microorganisms exist in the wastewater, and if the pathogenic microorganisms are not killed and removed, the wastewater poses great threats to the ecological environment and the human health. Therefore, the disinfection technology is the key to realize the regeneration and safe reuse of the sewage.

Conventional disinfection techniques mainly include disinfection using chemical disinfectants such as chlorine, ozone, chloramine, chlorine dioxide and the like and ultraviolet irradiation disinfection. However, the above disinfection methods have certain limitations in practical applications; for example, certain pathogens are naturally resistant to ultraviolet light or chlorine; the use of chlorine and ozone for sterilization may result in the production of sterilization by-products such as trihalomethanes, haloacetic acids and bromates. More importantly, many pathogens remain viable, exist in an uncultureable state after treatment by conventional sterilization methods, have certain characteristics of viable cells (e.g., cell integrity, metabolic activity or toxicity), and still present safety concerns. In order to overcome the limitations of the traditional disinfection method, further ensure the safety of water, and research and develop high-efficiency advanced disinfection technology with broad-spectrum and thorough sterilization effects is urgent.

Advanced oxidation technologies (AOPs) achieve pollution removal by generating free radicals with high oxidation activity, and have a significant effect on killing pathogenic bacteria. Persulfate is stable and mostly solid in the environment, convenient for transportation and storage, and activates SO generated from persulfate as compared with OH₄ ^·-The compound has higher oxidation-reduction potential (2.5-3.1V) and longer life span (30-40 mu s), and has obvious advantages on the inactivation performance of pathogenic bacteria, but how to activate persulfate is the core of the technology. Compared with the activation mode using external energy such as light, heat and the like, the method has the advantages that the energy consumption is reduced by using the catalyst to activate the persulfate, the operation is simple and convenient, and the practical application is easier. For example, Chinese patent application CN104909427A discloses a method for treating advanced oxidation technology by photo-assisted porous copper bismuthate activated persulfate water, which utilizes the characteristic crystal structure and double-element characteristics of copper bismuthate to realize the reinforced removal of refractory organic pollutants by generating hydroxyl radicals through photocatalysis and generating active oxidation substances through activating persulfate. However, most of the catalysts reported in this application or in the prior art require complicated synthetic routes and reagents or are costly, limiting their further use at this stage.

Therefore, there is an urgent need to develop a novel catalyst with high cost performance, high activity, high stability, and low cost, which is easily available, for persulfate activation, and thoroughly disinfection and sterilization of the recovered water resources.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects and shortcomings of complex synthetic routes and reagents required by existing persulfate catalysts and providing a novel catalyst which has high cost performance, high activity, high stability, low price and easy obtaining and is used for persulfate activation.

The invention aims to provide an application of a bismuth catalyst in sterilization and disinfection of activated persulfate.

The above purpose of the invention is realized by the following technical scheme:

the application of the bismuth catalyst in sterilization and disinfection of activated persulfate is characterized in that the bismuth catalyst is simple substance bismuth or bismuth oxide, the dosage of the persulfate is 1.0-10.0 mM, and the dosage of the bismuth catalyst is 0.5-10.0 mg/mL. The elemental bismuth or bismuth oxide may be prepared in the laboratory or may be commercially available.

Adding an oxidant persulfate into the solution to be treated, adding the bismuth catalyst after the persulfate is dissolved, and stirring for reaction. In the reaction system, the persulfate and the bismuth catalyst are contacted with each other, and the persulfate is activated by electron transfer to generate hydroxyl free radical (. OH) and sulfate free radical (SO)₄ ^·-) Superoxide radical (O)₂ ^·-) Singlet oxygen (¹O₂) And the active oxygen species attack the target strain, so that the cell wall of the target strain is broken, DNA leaks and is dissolved out, and the target strain finally dies. Wherein, the stirring can ensure that the catalyst is fully contacted with the persulfate, thereby better catalyzing the activation of the persulfate to generate sulfate radical (SO)₄ ^·-) Superoxide radical (O)₂ ^·-) And the like, so that the target strain is efficiently inactivated.

Preferably, the concentration of the strains in the solution to be treated is 3-7 logs₁₀ cfu/mL。

Further, the elementary bismuth is unprocessed elementary bismuth (Bi) or popcorn-shaped elementary bismuth (LNBi) processed by liquid nitrogen.

Further, the preparation method of the popcorn-shaped elemental bismuth comprises the following steps:

dissolving bismuth nitrate in nitric acid, fully stirring, adding ethylene glycol, and uniformly stirring; adding polyvinylpyrrolidone, stirring to completely disperse and dissolve the polyvinylpyrrolidone, performing hydrothermal reaction at 160-220 ℃, performing solid-liquid separation on the reaction liquid after complete reaction, and cleaning and drying the obtained solid to obtain simple substance bismuth; and treating the obtained simple substance bismuth by liquid nitrogen to obtain the bismuth-bismuth alloy.

Preferably, the relative molecular mass of the polyvinylpyrrolidone is 24000-40000. Preferably, the relative molecular mass of the polyvinylpyrrolidone is 24000-30000; more preferably, the polyvinylpyrrolidone has a relative molecular mass of 24000.

Preferably, the temperature of the hydrothermal reaction is 160-180 ℃, and more preferably, the temperature of the hydrothermal reaction is 160 ℃.

Preferably, the reaction time of the hydrothermal reaction is 8-48 h. Preferably, the reaction time of the hydrothermal reaction is 8-24 h; more preferably, the reaction time of the hydrothermal reaction is 24 h.

Preferably, the liquid nitrogen treatment is: placing the elementary bismuth material in a Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing on a magnetic stirrer for stirring, treating with liquid nitrogen for a period of time, and drying with a freeze dryer to obtain popcorn-shaped elementary bismuth full of cracks.

Preferably, the time of the liquid nitrogen treatment is 10-60 min. Preferably, the time for treating the liquid nitrogen is 10-30 min; more preferably, the time of the liquid nitrogen treatment is 30 min.

Preferably, the nitric acid has a concentration of 1M.

Preferably, the cleaning is repeated cleaning for multiple times by using ethanol and ultrapure water in sequence; and drying the mixture for 8 to 20 hours in an oven at the temperature of between 50 and 70 ℃.

Further, the bismuth oxide is bismuth oxide or bismuth oxyhalide.

Preferably, the bismuth oxide is α -Bi₂O₃Or beta-Bi₂O₃. The bismuth oxyhalide is BiOCl, BiOBr or BiOI.

Further, the alpha-Bi₂O₃The preparation method comprises the following steps:

adding Bi (NO)₃)₃·5H₂Dissolving O in nitric acid (1M), adding Cetyl Trimethyl Ammonium Bromide (CTAB), and stirring thoroughly; slowly dropping NaOH solution (0.21M), uniformly mixing, filtering, washing, drying, calcining at 320-370 ℃ for 2-3 h, and cooling to obtain the product alpha-Bi₂O₃。

Preferably, the calcining temperature is 350-370 ℃; more preferably, the calcination temperature is 350 ℃.

Further, the beta-Bi₂O₃The preparation method comprises the following steps:

s1, mixing Bi (NO)₃)₃·5H₂Dissolving O in nitric acid (1M), adding Cetyl Trimethyl Ammonium Bromide (CTAB), and stirring thoroughly; adding 0.4g of oxalic acid, mixing uniformly, filtering, washing, drying, calcining at 250-300 ℃ for 2-3 h, and cooling to obtain a product beta-Bi₂O₃。

Preferably, the calcining temperature is 270-300 ℃; more preferably, the calcination temperature is 270 ℃.

Further, the preparation method of BiOCl specifically comprises the following steps:

adding Bi (NO)₃)₃·5H₂Dissolving O in deionized water, adding saturated NaCl solution, and stirring completely and uniformly; transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the kettle into an oven, and carrying out hydrothermal reaction at 130-170 ℃; and after the autoclave is cooled to room temperature, washing the product with water and ethanol for 3 times, and then drying at 50-70 ℃ overnight to obtain the BiOCl.

Preferably, the temperature of the hydrothermal reaction is 150-170 ℃; more preferably, the temperature of the hydrothermal reaction is 150 ℃.

Preferably, the time of the hydrothermal reaction is 3-5 h, and more preferably, the time of the hydrothermal reaction is 4 h.

Further, the preparation method of the BiOBr specifically comprises the following steps:

adding Bi (NO)₃)₃·5H₂Adding O and KBr into the ethylene glycol solution (1M), and fully and uniformly stirring; transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the kettle into an oven, and carrying out hydrothermal reaction at 100-140 ℃; and after the autoclave is cooled to room temperature, washing the product with water and ethanol for 3 times, and then drying at 50-70 ℃ overnight to obtain the BiOBr.

Preferably, the temperature of the hydrothermal reaction is 120-140 ℃; more preferably, the temperature of the hydrothermal reaction is 120 ℃.

Preferably, the time of the hydrothermal reaction is 10-15 h, and more preferably, the time of the hydrothermal reaction is 12 h.

Further, the preparation method of the BiOI specifically comprises the following steps:

adding Bi (NO)₃)₃·5H₂Dissolving O in ultrapure water, dropwise adding KI (0.125M) under the condition of continuous stirring, and fully and uniformly mixing; transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the kettle into an oven, and carrying out hydrothermal reaction at 60-100 ℃; and after the autoclave is cooled to room temperature, washing the product with water and ethanol for 3 times, and then drying at 50-70 ℃ overnight to obtain the BiOI.

Preferably, the temperature of the hydrothermal reaction is 80-100 ℃; more preferably, the temperature of the hydrothermal reaction is 80 ℃.

Preferably, the time of the hydrothermal reaction is 3-5 h, and more preferably, the time of the hydrothermal reaction is 4 h.

Still further, the persulfate is Peroxymonosulfate (PMS) or Peroxydisulfate (PS). Preferably, the peroxymonosulfate is NaHSO₅、KHSO₅Or NH₄HSO₅The peroxodisulfate is Na S O, K₂S₂O₈Or (NH)₄)₂S₂O₈。

Further, the bacteria to be sterilized include, but are not limited to, escherichia coli (e.coli K-12), staphylococcus aureus (s.aureus), Salmonella (Salmonella), enterococcus faecalis (e.faecalis).

Furthermore, when the bismuth catalyst is used for activating persulfate to sterilize and disinfect, visible light irradiation is increased, and the irradiation condition of the visible light is that lambda is more than or equal to 420 nm.

The invention selects bismuth-series materials as catalysts, activates persulfate to generate a series of Reactive Oxygen Species (ROS) with high reactivity, and the substances further attack pathogenic microorganisms in water body to realize high-efficiency killing of the pathogenic microorganismsAnd (6) alive. Compared with other catalysts, the bismuth catalyst is easy to obtain, wide in source, low in cost, free of complex preparation process and good in application prospect. Further, bismuth oxide (. alpha. -Bi)₂O₃、β-Bi₂O₃BiOCl, BiOBr and BiOI) has excellent photocatalytic capacity, and is favorable for further activating persulfate under the visible light irradiation condition so as to improve the disinfection efficiency.

On the other hand, the bismuth catalyst has the advantages of simple preparation method, strong catalytic activity and good stability, and the method for sterilizing and disinfecting by activating persulfate and activating persulfate is simple and convenient to operate, thorough in sterilization, high in efficiency and free from generating a disinfection by-product; meanwhile, the material is easy to recover and can be recycled through regeneration, and is an environment-friendly material.

The invention has the following beneficial effects:

the bismuth-based material is selected as the catalyst, and the bismuth-based material is activated to generate a series of Reactive Oxygen Species (ROS) with high reactivity to attack pathogenic microorganisms in water body, so that excellent sterilization and disinfection effects are achieved; the sterilization efficiency can be further improved under the condition of visible light irradiation.

In addition, the bismuth catalyst is easy to obtain, the cost is lower, the preparation method is simple, the catalyst has stronger catalytic activity and better stability, the method for activating persulfate and activating persulfate to sterilize and disinfect is simple and convenient to operate, the sterilization is thorough, the efficiency is high, and no disinfection by-product is generated; meanwhile, after the catalyst is circularly catalyzed, the catalyst still can keep higher catalytic activity, is easy to recover and can be repeatedly used through regeneration, and is an environment-friendly material.

Drawings

Fig. 1 is a scanning electron microscope SEM image of the elemental bismuth catalyst prepared in example 1.

FIG. 2 is a scanning electron micrograph SEM of elemental bismuth catalyst treated with liquid nitrogen of example 6.

FIG. 3 is a SEM image of bismuth oxide prepared in example 15.

FIG. 4 is a SEM image of bismuth oxyiodide prepared in example 18.

FIG. 5 is an X-ray diffraction (XRD) pattern of elemental bismuth Bi prepared in example 1 and LNBi as the elemental bismuth catalyst treated with liquid nitrogen in example 6.

Fig. 6 is an X-ray diffraction (XRD) pattern of bismuth oxide prepared in example 14.

Fig. 7 is an X-ray diffraction (XRD) pattern of bismuth oxyiodide prepared in example 18.

FIG. 8 is an Electron Spin Resonance (ESR) spectrum of hydroxyl radicals and sulfate radicals of an elemental bismuth catalyst (LNBi) activated PS prepared in example 6.

FIG. 9 is the superoxide radical Electron Spin Resonance (ESR) spectrum of elemental bismuth catalyst (LNBi) activated PS prepared in example 6.

FIG. 10 is a singlet oxygen Electron Spin Resonance (ESR) spectrum of an elemental bismuth catalyst (LNBi) activated PS prepared in example 6.

FIG. 11 is a graph showing the comparison of the bactericidal performance of the PS-inactivated Escherichia coli activated by elemental bismuth prepared in examples 1, 6 and 13 and comparative examples 1 to 3.

FIG. 12 is a graph showing the comparison of the bactericidal activity of bismuth oxide prepared in examples 14 to 15 for activating PS and inactivating Escherichia coli alone.

FIG. 13 is a graph showing the comparison of bactericidal activity of PS-inactivated Escherichia coli activated with bismuth oxyhalide prepared in examples 16 to 18.

Detailed Description

The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.

Example 1A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying in a 60 ℃ oven for 12 hours to obtain the simple substance bismuth material.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 2A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass of 40000) into the mixed solution obtained in S2, and stirring for more than 30min to completely disperse the PVP and then dissolve the PVP;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying in a 60 ℃ oven for 12 hours to obtain the simple substance bismuth material.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 3A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 8 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying in a 60 ℃ oven for 12 hours to obtain the simple substance bismuth material.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 4A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 48 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying in a 60 ℃ oven for 12 hours to obtain the simple substance bismuth material.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 5A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 10min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 6A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂O dissolved in 10mL of 1Fully stirring in nitric acid of M;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 7A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 60min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 8A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (2.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 9A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (4.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 10A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) is mixed with a PS solution (10.0mM) and applied to Escherichia coli inactivation (in application example 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 11A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (2.0mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 12A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (10.0mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in application example 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Example 13A bismuth catalyst

The simple substance bismuth material is prepared by the following steps:

s1, mixing 0.364g Bi (NO)₃)₃·5H₂Dissolving O in 10mL of 1M nitric acid, and fully stirring;

s2, adding 55mL of glycol, mixing with the mixed solution in the S1, and stirring for 10min again;

s3, adding 0.6g of polyvinylpyrrolidone (PVP, relative molecular mass 24000) into the mixed solution obtained in S2, and stirring for more than 30min to dissolve the PVP after the PVP is completely dispersed;

s4, transferring the mixed solution obtained in the S3 into a high-pressure hydrothermal reaction kettle with a Teflon liner of 100mL, putting the kettle into an oven, and carrying out hydrothermal reaction for 24 hours at 160 ℃;

s5, performing solid-liquid separation on the mixture obtained through the hydrothermal reaction by centrifugation, pouring out supernatant, repeatedly cleaning the obtained solid by ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;

s6, placing the elementary bismuth prepared in the S5 into a 850mL Dewar flask, pouring liquid nitrogen for quenching treatment, adding a magnetic rotor, placing the mixture on a magnetic stirrer for stirring, treating the mixture for 30min by using liquid nitrogen, and drying the mixture by using a freeze dryer to obtain the popcorn-shaped elementary bismuth full of cracks.

The prepared elemental bismuth material (0.5mg/mL) was mixed with a PS solution (1.0mM) and irradiated with xenon (light having a wavelength of 420nm or less was filtered off with a filter) to inactivate Escherichia coli (application example 4, measurement of bactericidal activity of Escherichia coli (E. coli K12)).

Example 14A bismuth catalyst

The preparation method of the bismuth oxide material comprises the following steps:

s1 mixing 2.0g of Bi (NO)₃)₃·5H₂Dissolving O in 20mL of 1M nitric acid, adding 0.1g of hexadecyl trimethyl ammonium bromide (CTAB), and fully and uniformly stirring;

s2, slowly dropping 200mL of NaOH solution (0.21M), fully stirring, filtering the mixture in the solution, washing, and drying at 80 ℃ for 8 hours;

s3, putting the obtained dried sample into a muffle furnace, calcining for 2h at 350 ℃, and cooling to room temperature to obtain the alpha-Bi₂O₃。

Taking the prepared bismuth oxide material alpha-Bi₂O₃(0.5mg/mL) was mixed with a PS solution (1.0mM) and applied to inactivation of E.coli (application example 4, measurement of bactericidal activity of E.coli K12).

Example 15A bismuth catalyst

The preparation method of the bismuth oxide material comprises the following steps:

s1 mixing 2.0g of Bi (NO)₃)₃·5H₂Dissolving O in 20mL of 1M nitric acid, adding 0.1g of hexadecyl trimethyl ammonium bromide (CTAB), and fully and uniformly stirring;

s2, adding 0.4g of oxalic acid into the solution S1, fully stirring, filtering the mixture in the solution, washing the precipitate with ethanol and deionized water, and drying at 80 ℃ for 8 hours;

s3, putting the obtained dried sample into a muffle furnace, calcining for 2h at 270 ℃, and cooling to room temperature to obtain the beta-Bi₂O₃。

Taking the prepared bismuth oxide material beta-Bi₂O₃(0.5mg/mL) was mixed with a PS solution (1.0mM) and applied to inactivation of E.coli (application example 4, measurement of bactericidal activity of E.coli K12).

Example 16A bismuth catalyst

The preparation method of the bismuth oxychloride material comprises the following steps:

s1, mixing 1.94g Bi (NO)₃)₃·5H₂Dissolving O in 100mL of deionized water, adding 20mL of saturated NaCl solution, and fully and uniformly stirring;

s2, transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the high-pressure hydrothermal reaction kettle into an oven, and reacting for 4 hours at 150 ℃;

and S3, after the autoclave is cooled to room temperature, washing the obtained catalyst with water and ethanol for 3 times, and then drying at 60 ℃ overnight to obtain the BiOCl.

The prepared bismuth oxychloride material BiOCl (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to escherichia coli inactivation (in an application example, 4, escherichia coli (E.coli K12) sterilization performance determination).

Example 17A bismuth catalyst

The preparation method of the bismuth oxybromide material comprises the following steps:

s1, mixing Bi (NO) with a certain chemical dose ratio₃)₃·5H₂Adding O and KBr into 100mL of glycol solution (1M), and fully stirring;

s2, transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the high-pressure hydrothermal reaction kettle into an oven, and reacting for 12 hours at 120 ℃;

s3, washing the obtained catalyst with water and ethanol for 3 times, and then drying at 60 ℃ overnight to obtain the BiOBr.

The prepared bismuth oxybromide material BiOBr (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to escherichia coli inactivation (in an application example, 4, escherichia coli (E.coli K12) sterilization performance determination).

Example 18A bismuth catalyst

A bismuth oxyiodide material is prepared by the following steps:

s1, weighing 5mmol of Bi (NO)₃)₃·5H₂Dissolving O in 60mL of ultrapure water, dropwise adding 40mL of KI (0.125M) under the condition of continuous stirring, and fully and uniformly mixing;

s2, transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle with a Teflon liner, putting the high-pressure hydrothermal reaction kettle into an oven, and reacting for 4 hours at 80 ℃;

s3, washing the obtained catalyst with water and ethanol for 3 times, and then drying at 60 ℃ overnight to obtain the BiOI.

The prepared bismuth oxyiodide material BiOI (0.5mg/mL) is mixed with a PS solution (1.0mM) and applied to Escherichia coli inactivation (in an application example, 4, Escherichia coli (E.coli K12) sterilization performance measurement).

Comparative example 1

25mL of the suspension containing Escherichia coli at a concentration of 7log₁₀cfu/mL of the aqueous solution was added to a 50mL beaker with 12.5mg of the elemental bismuth material (0.5mg/mL) prepared in example 1, the beaker was placed in a 25 ℃ thermostatic waterbath magnetic stirrer, magnetic stirring was performed, 50. mu.L of the sample was taken when the reaction time reached 5min, 10min, 20min and 30min, the sample was uniformly spread on an LB-agar medium, the LB-agar medium was placed in a 37 ℃ thermostatic incubator for 12 hours, then the number of colonies on the medium was recorded, and the concentration of remaining viable Escherichia coli in the sample was calculated. See table 1 for results.

Comparative example 2

25mL of the suspension containing Escherichia coli at a concentration of 7log₁₀Aqueous solution of cfu/mLAdding 1mM PS into a 50mL beaker, placing the beaker into a 25 ℃ constant-temperature water bath magnetic stirrer, magnetically stirring, sampling 50 mu L when the reaction is carried out for 5min, 10min, 20min and 30min, uniformly coating the sample on an LB-agar culture medium, placing the sample into a 37 ℃ constant-temperature incubator for 12 hours, then recording the colony number on the culture medium, and calculating the concentration of the residual viable escherichia coli in the sampled sample. See table 1 for results.

Comparative example 3

25mL of the suspension containing Escherichia coli at a concentration of 7log₁₀Placing cfu/mL aqueous solution in a 50mL beaker, placing the beaker in a 25 ℃ constant temperature water bath magnetic stirrer, magnetically stirring, adding a xenon lamp for irradiation (filtering light with a filter to remove light with a wavelength of below 420nm), sampling 50 microlitres when the reaction reaches 5min, 10min, 20min and 30min, uniformly coating the sample on an LB-agar culture medium, placing the sample in a 37 ℃ constant temperature incubator for culturing for 12 hours, then recording the colony number on the culture medium, and calculating the concentration of the residual viable escherichia coli in the sampled sample. See table 1 for results.

Catalyst Performance test for application examples

1. SEM detection

Elemental bismuth prepared in example 1, elemental bismuth treated with liquid nitrogen in example 6, and bismuth oxide β -Bi prepared in example 15 were added₂O₃Scanning electron microscope SEM detection is carried out on the bismuth oxyiodide material prepared in the embodiment 18, and the detection results are shown in figures 1-4.

As can be seen from the figure: the elemental bismuth material prepared in example 1 is spherical, has a smooth surface and an average particle size of about 500 nm; in example 6, the surface of elemental bismuth treated by liquid nitrogen becomes rough, cracks and chips appear, and the surface is popcorn-shaped; the bismuth oxide prepared in example 15 and the bismuth oxyiodide prepared in example 18 were flower-shaped and consisted of nanorods and nanosheets, respectively.

2. X-ray diffraction (XRD) testing

The elemental bismuth material prepared in example 1, the elemental bismuth treated with liquid nitrogen in example 6, the bismuth oxide prepared in example 14, and the bismuth oxyiodide prepared in example 18 were subjected to X-ray diffraction analysis, and the obtained XRD spectrogram is shown in fig. 5 to 7.

It can be seen from the figureBoth the elemental bismuth prepared in example 1 and the elemental bismuth treated by liquid nitrogen in example 6 have XRD spectra which correspond well to PDF card of elemental bismuth, further demonstrating the success and effectiveness of the preparation method of the elemental bismuth material. FIG. 6 shows that the bismuth oxide prepared in example 14 is α -Bi₂O₃. The bismuth material prepared in example 18 of fig. 7 was matched to the PDF card of the bio i, demonstrating that the material was a bio i.

3. ESR test

In order to fully prove the catalytic activation effect of bismuth material on PS, DMPO is adopted as a capture reagent to detect SO of different systems₄ ^·-OH and O₂ ^·-Detecting different systems of singlet oxygen by using TEMP as capture reagent¹O₂) ESR measurements were performed on the elemental bismuth material prepared in example 6, and the results are shown in fig. 8 to 10.

As can be seen, stronger DMPO-OH signals are detected in the simple substance bismuth (LNBi)/persulfate system; furthermore, DMPO-SO₄ ^·-、DMPO-O₂ ^·-And TEMP-¹O₂The signal is also successfully detected. These results indicate that elemental bismuth (LNBi) successfully activates PS to produce OH, SO₄ ^·-，O₂ ^·-And¹O₂。

4. coli (e.coli K12) bactericidal performance assay

25mL of the suspension containing Escherichia coli at a concentration of 7log₁₀Adding PS with a certain dose and the bismuth catalyst prepared in the examples 1-18 into a 50mL beaker from cfu/mL aqueous solution, placing the beaker into a 25 ℃ constant-temperature water bath magnetic stirrer, magnetically stirring, sampling 50 mu L when the reaction is carried out for 5min, 10min, 20min and 30min, uniformly coating the sample on an LB-agar culture medium, placing the sample into a 37 ℃ constant-temperature incubator for culturing for 12 hours, then recording the colony number on the culture medium, and calculating the concentration of the residual viable escherichia coli in the sample. See table 1 for results.

TABLE 1 measurement results of bactericidal properties of bismuth catalysts (bactericidal time 30min)

Group of	Number of bacteria killed (log10 cfu/mL)	Group of	Number of bacteria killed (log10 cfu/mL)
				Example 1	2.1	Example 12	2.5
Example 2	1.2	Example 13	4.9
				Example 3	0.9	Example 14	1.5
Example 4	1.3	Example 15	4.4
				Example 5	2.8	Example 16	4.5
Example 6	3.6	Example 17	4.5
				Example 7	3.3	Example 18	5.8
Example 8	3.9	Comparative example 1	0.06
				Example 9	4.6	Comparative example 2	0.1
Example 10	5.5	Comparative example 3	0.2
				Example 11	3.7

As can be seen from table 1, elemental bismuth prepared using PVP with a molecular weight of 24000 (example 1) has superior bactericidal properties to elemental bismuth prepared using PVP with a molecular weight of 40000 (example 2). Comparing example 1 with examples 3 to 4, it can be seen that the hydrothermal reaction time in the preparation process has an influence on the effect of activating PS to inactivate escherichia coli by elemental bismuth, and that too short hydrothermal reaction time (example 3) or too long hydrothermal reaction time (example 4) is not beneficial to improving the catalytic bactericidal performance of elemental bismuth. In the embodiments 5 to 13, the elemental bismuth prepared in the embodiment 1 is further processed by using liquid nitrogen, and after the liquid nitrogen processing, the sterilization performance of the elemental bismuth activated PS on escherichia coli is obviously improved. Examples 5 to 7 examine the influence of the liquid nitrogen treatment time on the sterilizing performance of the elemental bismuth, and preferably select the optimal liquid nitrogen treatment time to be 30min (example 6). Examples 8-12 have carried out a series of studies of bactericidal performance through changing the dosage of PS and simple substance bismuth, and the result shows, increase PS concentration in the system can promote the sterilization effect, and increase dosage of simple substance bismuth can promote the promotion of sterilization effect within a certain range, and excessive simple substance bismuth is thrown and is unfavorable for the complete inactivation of escherichia coli instead. The bismuth oxide (examples 14-15) and bismuth oxyhalide materials (examples 16-18) of the invention are also used as catalysts to activate PS to inactivate Escherichia coli, and the bactericidal performance of the materials of examples 15-18 is above 4.4log10 cfu/mL.

The bactericidal effect of examples 1, 6, and 13 and comparative examples 1 to 3 with respect to the reaction time is shown in fig. 11. As can be seen from the figure, the single bismuth, the single PS and the single visible light (lambda is more than or equal to 420nm) systems have no obvious sterilization effect (comparative examples 1-3); when Bi is mixed with PS, Bi can activate PS to kill 2.1log in 30min₁₀cfu/mL of E.coli (example 1); after 30min of liquid nitrogen treatment of elemental bismuth prepared in example 1 (example 6), the killing of E.coli was increased to 3.6log₁₀cfu/mL (30min), which shows that elemental bismuth treated with liquid nitrogen can enhance the PS activating ability. On the other hand, after the light with the wavelength of more than 420nm is introduced, the killing of the Escherichia coli can be further promoted to about 4.9log within 30min₁₀cfu/mL, which shows that illumination can promote the activation of Bi on PS, thereby improving the inactivation capacity of the reaction system on Escherichia coli.

The change of the bactericidal effect of the bismuth oxide activated PS inactivated Escherichia coli (examples 14 to 18) with the reaction time is shown in FIGS. 12 to 13. As can be seen from FIG. 12, the α -Bi compounds prepared in examples 14 to 15 were used alone₂O₃And beta-Bi₂O₃Hardly reaching the purpose of inactivating escherichia coli, and alpha-Bi is added within 30min after PS is added₂O₃Can kill about 1.5log₁₀cfu/mL of E.coli, and beta-Bi₂O₃The sterilization capability of the PS system reaches 4.5log₁₀cfu/mL. FIG. 13 shows that the effect of the activated PS of the bismuth oxyhalide material prepared in examples 16 to 18 on the inactivation of Escherichia coli, and BiOCl and BiOBr can kill about 4.5 logs within 30min₁₀cfu/mL E.coli, while BiOI killed 5.8log₁₀The effect is better for cfu/mL escherichia coli. The results show that the bismuth oxide materials prepared in examples 14-18 can be used as catalysts to activate PS for sterilization and disinfection.

In conclusion, the bismuth catalysts can successfully activate persulfate to kill escherichia coli, and have a remarkable disinfection effect.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.