CN113600173B - Application of bismuth catalyst in sterilization and disinfection by activating persulfate - Google Patents
Application of bismuth catalyst in sterilization and disinfection by activating persulfate Download PDFInfo
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- CN113600173B CN113600173B CN202110927341.3A CN202110927341A CN113600173B CN 113600173 B CN113600173 B CN 113600173B CN 202110927341 A CN202110927341 A CN 202110927341A CN 113600173 B CN113600173 B CN 113600173B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 151
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 57
- 230000003213 activating effect Effects 0.000 title claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 13
- IYNWNKYVHCVUCJ-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi] IYNWNKYVHCVUCJ-UHFFFAOYSA-N 0.000 claims description 148
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 82
- 241000588724 Escherichia coli Species 0.000 claims description 80
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 72
- 239000007788 liquid Substances 0.000 claims description 56
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 50
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 25
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 23
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical group [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 2
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 63
- 230000001954 sterilising effect Effects 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 16
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- 239000011259 mixed solution Substances 0.000 description 45
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 13
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- 230000000052 comparative effect Effects 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical group Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 8
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 6
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000004976 peroxydisulfates Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000194032 Enterococcus faecalis Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 241000607142 Salmonella Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 241000482268 Zea mays subsp. mays Species 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241001646716 Escherichia coli K-12 Species 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- B01J23/18—Arsenic, antimony or bismuth
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
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.
Description
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; sterilization using chlorine and ozone 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 water safety, 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 in the environment, is mostly solid, is convenient for transportation and storage, and activates SO generated from persulfate compared with OH4 ·-Has higher oxidation-reduction potential (2.5-3.1V) and longer life span (30-40 mus) 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, and the method comprises the steps ofThe method utilizes the characteristic crystal structure and the double-element characteristics of copper bismuthate to carry out photocatalysis to generate hydroxyl radicals and activate persulfate to generate active oxidation substances, thereby realizing the reinforced removal of refractory organic pollutants. 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 application of a bismuth catalyst in sterilization and disinfection by activating persulfate.
The above purpose of the invention is realized by the following technical scheme:
the bismuth catalyst is used for activating persulfate to sterilize and disinfect, the bismuth catalyst is simple substance bismuth or bismuth oxide, the consumption of the persulfate is 1.0-10.0 mM, and the consumption 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 make the catalyst fully contact with the persulfateThereby better catalyzing the persulfate activation 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 strain in the solution to be treated is 3-7 log10 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 hydrothermal reaction is carried out at a temperature of 160 to 180 ℃, and more preferably, the hydrothermal reaction is carried out at a temperature of 160 ℃.
Preferably, the reaction time of the hydrothermal reaction is 8 to 48 hours. Preferably, the reaction time of the hydrothermal reaction is 8-24 h; more preferably, the reaction time of the hydrothermal reaction is 24h.
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 to 60min. Preferably, the time for treating the liquid nitrogen is 10-30 min; more preferably, the time of the liquid nitrogen treatment is 30min.
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 a drying 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), mixing uniformly, filtering, washing, drying, calcining at 320-370 ℃ for 2-3 h, 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, adding Bi (NO)3)3·5H2Dissolving O in nitric acid (1M), adding Cetyl Trimethyl Ammonium Bromide (CTAB), and stirring thoroughly; adding 0.4g oxalic acid, mixing evenly, filtering, washing, drying, calcining for 2-3 h at 250-300 ℃, cooling to obtain the 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 inner container, putting the kettle into an oven, and feeding the mixture into the oven at 130-170 DEG CCarrying out hydrothermal reaction; 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 BiOCl.
Preferably, the temperature of the hydrothermal reaction is 150-170 ℃; more preferably, the temperature of the hydrothermal reaction is 150 ℃.
Preferably, the hydrothermal reaction time is 3 to 5 hours, and more preferably, the hydrothermal reaction time is 4 hours.
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 to 15 hours, and more preferably, the time of the hydrothermal reaction is 12 hours.
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 hydrothermal reaction time is 3 to 5 hours, and more preferably, the hydrothermal reaction time is 4 hours.
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 for sterilization and disinfection 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 for sterilization and disinfection, visible light irradiation is increased, wherein the irradiation condition of the visible light is that lambda is more than or equal to 420nm.
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 inactivation of the pathogenic microorganisms. 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 preparation method of the bismuth catalyst is simple, has stronger catalytic activity and better stability, and the method for sterilizing and disinfecting by activating persulfate and activating persulfate has the advantages of simple and convenient operation, thorough sterilization, high efficiency and no generation of disinfection by-products; 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 cyclic catalysis, the catalyst can still maintain higher catalytic activity, is easy to recover, 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 comparing 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 E.coli alone.
FIG. 13 is a graph showing the comparison of bactericidal activity of PS-inactivated Escherichia coli activated by bismuth oxyhalide prepared in examples 16 to 18.
Detailed Description
The invention is further described with reference to the drawings and specific examples, 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying in an oven at 60 ℃ for 12 hours to obtain the simple substance bismuth material.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene glycol, mixing with the mixed solution in the S1, and stirring for 10min again;
s3, adding 0.6g of polyvinylpyrrolidone (PVP, the relative molecular mass is 40000) into the mixed solution obtained in the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 through centrifugation, pouring out the supernatant, repeatedly washing the obtained solid with ethanol and ultrapure water for multiple times in sequence, and drying in an oven at 60 ℃ for 12 hours to obtain the simple substance bismuth material.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 through centrifugation, pouring out the supernatant, repeatedly washing the obtained solid with ethanol and ultrapure water for multiple times in sequence, and drying in an oven at 60 ℃ for 12 hours to obtain the simple substance bismuth material.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying in an oven at 60 ℃ for 12 hours to obtain the simple substance bismuth material.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 the 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 step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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)3·5H2Dissolving O in 10mL of 1M nitric acid, and fully stirring;
s2, adding 55mL of ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the elemental 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 with the liquid nitrogen for 30min, and drying the mixture by using a freeze dryer to obtain the popcorn elemental bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the S3 to a high-pressure hydrothermal reaction kettle with a 100mL Teflon liner, 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (2.0 mM) and applied to Escherichia coli inactivation (in an application example, 4, escherichia coli (E.coli K12) sterilization performance determination).
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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (4.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the S3 to a high-pressure hydrothermal reaction kettle with a 100mL Teflon liner, 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (10.0 mM) and applied to Escherichia coli inactivation (in an 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (2.0 mg/mL) is mixed with a PS solution (1.0 mM) 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 ethylene 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the elemental 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 with the liquid nitrogen for 30min, and drying the mixture by using a freeze dryer to obtain the popcorn elemental bismuth full of cracks.
The prepared elemental bismuth material (10.0 mg/mL) is mixed with a PS solution (1.0 mM) and applied to Escherichia coli inactivation (in an 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 the S2, and stirring for more than 30min to completely disperse and dissolve the PVP;
s4, transferring the mixed solution obtained in the step S3 to 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 using ethanol and ultrapure water for multiple times in sequence, and drying the solid in a 60 ℃ oven for 12 hours;
and S6, placing the simple substance 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 simple substance bismuth full of cracks.
The prepared elemental bismuth material (0.5 mg/mL) is mixed with a PS solution (1.0 mM) and irradiated by a xenon lamp (light with the wavelength of below 420nm is filtered by a filter) to be applied to escherichia coli inactivation (application example 4, measurement of the bactericidal performance 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 and washing the mixture in the solution, and drying at 80 ℃ for 8 hours;
s3, placing the obtained dried sample into a muffle furnace, calcining for 2 hours at 350 ℃, and cooling to room temperature to obtain the alpha-Bi2O3。
Taking the prepared bismuth oxide material alpha-Bi2O3(0.5 mg/mL) was mixed with a PS solution (1.0 mM) 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 in the S1, fully stirring, filtering a mixture in the solution, washing a precipitate with ethanol and deionized water, and drying at 80 ℃ for 8 hours;
s3, placing the obtained dried sample into a muffle furnace, calcining for 2 hours at 270 ℃, and cooling to room temperature to obtain the beta-Bi2O3。
Taking the prepared bismuth oxide material beta-Bi2O3(0.5 mg/mL) was mixed with a PS solution (1.0 mM) 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 of Bi (NO)3)3·5H2O is dissolved inAdding 20mL of saturated NaCl solution into 100mL of deionized water, 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 (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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, adding 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 ℃;
and S3, washing the obtained catalyst with water and ethanol for 3 times, and drying at 60 ℃ overnight to obtain the BiOBr.
The prepared bismuth oxybromide material BiOBr (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 ℃;
and S3, washing the obtained catalyst with water and ethanol for 3 times, and drying at 60 ℃ overnight to obtain the BiOI.
The prepared bismuth oxyiodide material BiOI (0.5 mg/mL) is mixed with a PS solution (1.0 mM) 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 (0.5 mg/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 7log10Adding 1mM PS into a 50mL beaker of 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.
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 420 nm), 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 added2O3And the scanning electron microscope SEM detection of the bismuth oxyiodide material prepared in example 18, the detection results are shown in fig. 1 to 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 500nm; 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 XRD spectra obtained are shown in fig. 5 to 7.
As can be seen from the figure, the XRD spectrogram of the elemental bismuth prepared in example 1 or the elemental bismuth treated by liquid nitrogen in example 6 corresponds well to the PDF card of the elemental bismuth, and further shows that the preparation method of the elemental bismuth material is successful and effective. 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 carried out 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 resultsShows that the simple substance bismuth (LNBi) successfully activates PS to generate OH and SO4 ·-，O2 ·-And1O2。
4. coli (E.coli K12) bactericidal Property measurement
25mL of the suspension containing Escherichia coli at a concentration of 7log10Adding a certain amount of PS 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 lasts for 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 active escherichia coli in the sample. See table 1 for results.
TABLE 1 measurement results of bactericidal properties of bismuth catalysts (bactericidal time 30 min)
| Group of | Number of germs (log 10 cfu/mL) | Group of | Number of germs (log 10 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 examined the influence of the liquid nitrogen treatment time on the sterilizing performance of elemental bismuth, and the optimum liquid nitrogen treatment time was preferably 30min (example 6). Examples 8 to 12 have carried out a series of studies on sterilization performance by changing the addition of PS and bismuth, and the results show that increasing the PS concentration in the system can enhance the sterilization effect, while increasing the addition of bismuth within a certain range can enhance the sterilization effect, and excessive addition of bismuth is not beneficial to complete inactivation of escherichia coli. The bismuth oxide (examples 14-15) and bismuth oxyhalide materials (examples 16-18) of the present invention were also used as catalysts to activate PS to inactivate E.coli, and the bactericidal properties of the materials of examples 15-18 were all 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. From the figure canThe single bismuth, the single PS and the single visible light (lambda is more than or equal to 420 nm) 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 (example 6) of elemental bismuth prepared in example 1, the coliform killing rate was increased to 3.6log10cfu/mL (30 min), 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 within 30min can be further promoted to about 4.9log10cfu/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) according to the present invention with the reaction time is shown in FIGS. 12 to 13. As is clear from FIG. 12, α -Bi prepared in examples 14 to 15 was 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 the effect of PS activation on Escherichia coli of bismuth oxyhalide materials prepared in examples 16 to 18, and BiOCl and BiOBr can kill about 4.5log in 30min10cfu/mL E.coli, while BiOI killed 5.8log10The effect is better for cfu/mL escherichia coli. The above results show that the bismuth oxide materials prepared in examples 14 to 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.
Claims (5)
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 dosage of the persulfate is 1.0 to 10.0mM, and the dosage of the bismuth catalyst is 0.5 to 10.0 mg/mL;
the simple substance bismuth is unprocessed simple substance bismuth or popcorn-shaped simple substance bismuth processed by liquid nitrogen; the bismuth oxide is bismuth oxide or bismuth oxyhalide;
the persulfate is peroxymonosulfate or peroxydisulfate;
when the bismuth catalyst is used for activating persulfate for sterilization and disinfection, visible light irradiation is added, wherein the irradiation condition of the visible light is that lambda is more than or equal to 420 nm;
the bacteria for sterilization and disinfection are escherichia coli.
2. The use according to claim 1, 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, carrying out hydrothermal reaction at 160-220 ℃, carrying out 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.
3. The use according to claim 2, wherein the polyvinylpyrrolidone has a relative molecular mass of 24000 to 40000.
4. The use according to claim 2, wherein the reaction time of the hydrothermal reaction is 8 to 48 hours.
5. The use according to claim 2, wherein the time of the liquid nitrogen treatment is 10 to 60min.
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